呂1俳氏41 (課程博士(英文))Date of submission (month day, year)

January 7,2022

Department ofApplied chemistry andS加dentlDNumber

DB1831

Life science

Yoshihiro sAITOSupervisors

Ohjiro suMIYA

Applica11t's name

Akihiko N仏TSUMOTO
KazunoriTAKAS印MA

Abstract (Doctor)
Title ofThesis

Retention Behavior of polycyclic Aromatic Hydrocarbons on Novel polymer・Based
Stationary phases in High perfonnance Liquid chromatography

Approx.80o words
Liquid chromatography (LC) is a powerful and convenienttechnique in the field ofanalytical chemistw
for the separation and determination of complex sample mixtures. The stationary phase in Lc plays animportant role, especia11y, octadecylsilica (ODS) stationary phases have been widely used in Lc because of
its high versatiliw, separation perfonnance and reasonable cost. However, ODs stationary phases sti11
have a several problems to be solved, such as less heavchemical resistance. 1n addition,it is necessary forthe development ofa new stationary phase which has a different selectivity 介om conventional oDs phases.
On t11e basis ofthe above background, the several wpes of synthetic polymeric materials, which has a highheavchemical resistance, have been applied as a stationary phase in Lc as we11 as in gas C11romatography(GC). 1n this thesis, novel polymer・based particles have been introduced as the stationary phase in high
Perfomance LC, and the retention behaviors on these stationary phases have been examined by using
Polycyclic aromatic hydrocarb0船(PAHS) aS 伽e sample analytes.

In chapter l, generaHn廿oduction ofthis thesis is described along 、vith the background ofthis 、Ⅳork.
In chapter 2, spherical particles ofcopolymers, polyimide (PD, was introduced as the stationary phase inLC, and 血e retention behavior of pAHs was compared xvith that of wpical oDs stationary phases.1naddition, the heat・resistance of the pl stationary phase was exalnined by elevating the column temperature

Up t0 100゜C. The plis prepared with the staHing materials of pyrome11itic dianhydride (PNIDA) and
4,4'・diaminodゆhenyl ether(4,4'・oxydianiline, ODA), resulting the spherical pl(PMDA・ODA wpe) parricles
With an average diameter of about 5 μm. The chromatographic results ofthe plstationary phase showed
the signi丘Cantly larger retentiviw ofpAHs than that ofoDs stationary phases, while the retention tendency
Ofpl phase for pAHs was silnilar to oDs phases. From the experiments ofthe column temperature up to100゜C,it 、vas confimled a good high・temperature stabiHty ofthe pl phase. A larger retention on the pl

Phase could be a杜ributed to the surface structure of the pl particles, because a number of aromaticfunctionalities are existed in the chemical structure ofthe polymer backbone、In chapter 3, another type of polymeric material, poly(benzoguanamine・CO・formaldehyde)(BF)、vasapplied to the stationary phase in LC. The BF has a good heavchemicalresistance which can be appHed as
matting agent, car paint, and toner additive.1he spherical BF particle has an average diameter of about 5μm. The retention behavior ofpAHs on the BF stationary phase was systematicaⅡy compared with that ofa commercia11y・available oDs and phenylbuwlsilica (PBS) stationary phases. The pBs phase shows
Similar retention behavior to the oDs phase.1n contrast, the retention behavior study for the BF phase
SholNs its di丘'erent selectivity from that ofthe oDs and the pBs phases. The results suggestthat the BF
Phase has the retentivity mainly on the basis of hydrophobic interaction between the stationary phase
Iigands and the solute molecule. on the basis of the comparison with the pBs phase which has aretentivity by these pheny11igands, the unique selectiviw of the BF phase could be attributed to therestricted movement ofthe pheny11igands.

In chapter 4, poly(benzoguanamine・CO・melalnine・CO・formaldehyde)(BNIF), where melamine isadditiona11y introduced as one of the starting materials of the copolymer along 、vith benzoguanamine andformaldehyde, was applied to the Lc stationary phase, and the retention behavior of pAHs on BMF
Stationary phase was compared with typical oDs and the BF stationary phases. The BMF is a co・polymer
Of BF and melamine, which has a good heavchemical resistance that can be applied as matting agent, carPaint, and toner additive as weⅡ as BF. The spherical BNIF particle has an average dialneter is about 9.5

μm. The retention behavior ofpAHs on the BNIF stationary phase was systematica11y compared with thatOf a commercia11y、available oDs and the BF phase. Although a similar retention behavior on the BF
Phase was observed on the BNIF phase, atthe salne time,the BNIF phase shows di丑'erentretention behavior
from that of oDs phase. A sma11er retentivity for some pAHS 、vas found on the BMF phase when
Comparing with the BF phase.1he results suggestthat the BMF phase has a retentivity on the basis ofhydrophobic interaction between the stationaly phase ligands and the solute molecule as found on the BF
Phase.1t is considered that distance ofpheny11igands ofthe BMF phase are further apart from each otherthan those of the BF phase, inducing a more interaction with analyte compounds with a ceHain molecularIength.

Fina11y, the over、a11 Conclusion ofthis thesis is summarized in chapter 5. These novel polymer・based
Stationary phases showed a characteristic selectivity, which is somewhat di行'erent from the selectivity on
typical oDs phases. These results suggestthat novel polymer・based stationary phase could be developed
On the basis of a systematic consideration of the retention behavior. Taking advantage of the uniqueretentivity of these novel polymer・based stationary phases, the development of new sample preparation
device is also expected.