別紙41 信果程博士(英文))Date of submission (month day, year)

July 8,2021

Departmen{ ofApplied cl〕en]istl}' andS加del]11D NumbelLife science

DB1838

Yoshihil'O SAITO
Supervisors

KokiNAILへ、GAMI

APP11Cant's nanw

Akihiko MATSUMOTO
KazunoriTA1島へSHIMA

Abstract (Doctor)
Title ofThesis

Extraction al〕d separation Media with syntl)etic polymers for High performance
C1Ⅱ'omatographic Analysis

Approx.80o words
Chromatography is a high・perfonnance separation technique that is colnn)only used in a
Variety of fields, induding the medical, environlnental, and food industries. LiquidChron〕atography (LC) is a representative technique of chromatographic methods that uses aIiquid, such as organic solvents, as the mobile phase for the separalion. 11) gas
Chromatography (GC), which is carried out with a gaseous the mobile phase, an efficient
Separation P引formance can be achieved especiaⅡy for the seP砥'ation of complex samplen)ixtures consisted of closely・related volatile organic con〕pounds. Recently, therequirements for analyticaltechniques in separation science have been significantly increased
On the basis ofthe enhanced demands for these methods.1he development of appropri飢eSeP砥'ation and exu'aclion lnedia designed for the target analytes has been signi負Canuy desired
In chromatographic analysish〕 this thesis, several synthetic polymers have been introduced as exu'action andSePω'ation media for l)igh performance chromatographic analysis
First, a poly(4・vinylpyridine)(P4VP) stationary phase has been inttoduced as separation
media in LC, and the molecular shape selectivity for a group of polycycHc aromaticCompounds (PACS) on P4Vp phase was evaluated.1he results was comP砥'ed with thatObtained on conventional chemicaⅡy・bonded stationary phases. 1n contrast to a
Conventional octadecylsilica (ODS) phase, the chemical structure of the P4Vp phase isConsisted of Hnear poly(4・vinylpyridil〕e) on a silicagel support. on the P4Vp phase, a highIinear correlation between the logari11〕mic retention factor and F number was observed for
Planar pACS, and smaⅡerretention for non・planar pAcs was also observed than planar pACS
Ihe selectivity for planar/non・planer analytes on the P4Vp phase was significanuy better tl〕anthat of a conventional polymeric oDS

Another stationary phase on the basis of a different type of synthetic polymer, aPoly(butylene terephthalate)(PBT)・coated silica has also been applied to the stauonary phasein LC. The retention trends for various aromatic compounds on the pBl phase were studied
along ＼¥itl〕 the effect of column temperature on the retention behavior. 1n the case of thePBT stationary phase, a good selectivity for planar/non・planar analytes was observed for
PACS. The trend 圦7as quite similar to that of the P4Vp stationary phase described above
HO＼Never, retention trend on the pBl phase sho＼Ned that "rod・1ike" molecules were retained
10nger than "sqU釦'e・1ike" molecules, suggesting a different separation mechanisn〕 between
P4Vp and pBl phases. 1n addition, the selectivity for quinoline/isoquinoline on the pBT
Stationary phase was better tl〕an that on the conventional station雛'y phases.1he resuHS
Suggestthatthe pBT recognizes the position ofthe nitrogen atom in the analyte molecule
Next, synthetic flbrous polyin〕ide (PD has been introduced as a separation medium inGC. Fiber・packed capi11ary column was prepared by packing the pl filaments into afused・siHca capiⅡary and d〕e retention performance as a Gc stationary phase was studied
In the pl phase, a good Hnear relationsl〕ip between the C砥'bon number and the logarithmic
retention factors of alkane analytes was observed along with linear van't Hoff plots where the10garithmic retention factors 、Nas plotted against the reciprocal absolute column {elnperature
Iaking adval〕tage of the synthetic pl filaments ＼vith a good heat・resistance,
temperature・progralnmed Gc sePω'ations with the 負brous pl stationary phase 入Vas
demonstrated

Synthetic fHaments have been also applied as the extraction n〕ediLun for the Gc analysis
Of n〕onoethanolamine (1YIEA), one of the hazardous volatile organic compounds in airSamples

Simultaneous extraction and derivatization process Was studied with theSpecia11y・designed needle・type device packed with fibrous zylon as tl〕e exlraction mediun〕
Furthermore, tl〕e needle・type device ＼Nas applied to tl〕e sample prePω'ation of other volatilean〕1nes
Introducing derivatization reaction with cyclohexanone, the sensitivity of NIEA
＼Nas significantly ilnproved, and the lnethod was possible to be applied to tl〕e salnple
PreP砥'ation of oth飢' volatile amines exisled il〕 air samples. Taking advantage of d)eSpecia11y・designed needle, the needle was able to be stored for several days at rooln
telnperature after the sampling, wh飢'e d〕e derivatives of the volatile amines were stably
trapped on the surface ofthe zylon filaments in the needle
Introducing braided arrangements with zylon filaments as an extraction lnedium, further
Possibilities of synthelic fibrous lnartials ＼Nere studied. preconcentration of arolnaticCon〕pounds in water samples with the braided extraction medium was establisl〕ed. ByCOIU〕ecting lnetal wire inside of the braid to a power supply and applying voltage to the wire,
hcat・assisted desorption with resistive heating was delnonstrated. on the basis of a low
V011age application to the n〕elal wh'e in u〕e center of bl'aided fiber as a extraction mediuln, thetelnperature of the eXれ'action capiⅡω'y was elevated and tl〕e desorption efaciency was clearlyH〕〕PI'oved by applying a v011age dunng the desorption process