7.
1 Radioisotopic Study of Methanol Transformation over H- and Fe-Beta Zeo-
lites; Influence of Si/Al Ratio on Distribution of Products
É. Sarkadi-Pribóczki, N. Kumar a) , D.Yu. Murzin a) and Z. Kovács
The acid-basic properties of Beta zeolite
can be modified by dealumination and/or ion-
exchange. The wide-pore H-Beta zeolite has
strong Brønsted acid sites and other chemi-
cal environment which govern adsorption and
conversion of methanol to dimethyl ether and
hydrocarbons during catalysis [1-2]. Partly
Fe-ion-exchanged Beta i.e. Fe-H-Beta zeolite
keeps this behavior to a certain extent; how-
ever, the presence of Fe ions can modify the
reaction pathway. In the present work, the
methanol conversion was studied over H- and
Fe-Beta zeolites at two different Si/Al ratios.
11 C-methanol was used to follow-up adsorp-
tion as well as desorption of methanol and its
derivates. Therefore, a radioactivity detector
was integrated to the gas chromatograph for
exact identification of the labelled methanol
and its derivates.
H-Beta and Fe-Beta zeolites were applied
at two different Si/Al ratios i.e. H-Beta(25)
and H-Beta(300) and Fe-H-Beta(25) and Fe-
H-Beta (300), respectively. A glass tube fixed-
bed reactor was used as a closed static reactor.
The 11 C-radioisotope (T1/2 =20.4 min) was
produced in 11 C-labelled carbon dioxide form
by cyclotron. The 11 C-methanol tracer was
produced by radiochemical process [3]. The
mixture of 11 C-methanol and non-radioactive
methanol was then introduced into zeolite by
He gas flow. The volatile products of catalytic
conversion of 11 C-methanol were analyzed by
radio-gas chromatography (gas chromatograph
with flame ionization detector (FID) coupled
on-line with a radioactivity detector).
The methanol conversion rate and prod-
uct selectivities to dimethyl ether, hydrocar-
62
bons (methane, C2 -C6 olefins and paraffins),
formaldehyde and carbon-oxides were mea-
sured and calculated over H- and Fe-Beta ze-
olites at two different Si/Al ratios at 250 and
350 ◦ C.
Over H-Beta(25) C2 -C6 hydrocarbons
(mostly as alkanes) with high conversion rate
and some dimethyl ether were detected due to
presence of strong Brønsted acid sites (∼270
µmol/g). Contrary, over H-Beta(300) a neg-
ligible amount of above gas products was de-
tected at 250 ◦ C due to less Brønsted acid sites
(∼82 µmol/g). At higher temperature (350 ◦ C)
the methanol conversion rate increased result-
ing in higher selectivity to C1 -C2 and higher
olefin/paraffin product ratio over H-Beta(300)
compared to H-Beta(25).
Over Fe-modified Beta zeolite as a bifunc-
tional beta zeolite the methanol conversion rate
was high with high selectivity to dimethyl ether
and only small amount of hydrocarbons (irre-
spectively of Si/Al ratios) was formed at 250
◦ C. Nevertheless, formaldehyde as an addi-
tional product was detected at 350 ◦ C besides
lower amounts of ether and hydrocarbons due
to the presence of Fe-ion and reduced acidity.
a) Laboratory of Industrial Chemistry, Process Chem-
istry Centre, Åbo Akademi University, FIN-
20500 Åbo / Turku, Finland
[1] Hunger M. and Horvath T., Catalysis Letters 49
(1997) 95.
[2] Tsoncheva T. and Dimitrova R., Applied Catalysis
A: General 225 (2002) 101.
[3] Sarkadi-Pribóczki É., Kumar N., Salmi T., Kovács
Z. and Murzin D. Yu., Catalysis Letters 93
(2004) 101.
7.2 Ion beam microanalysis of human hair follicles
Zs. Kertész, Z. Szikszai, P. Pelicon a) , J. Simčič a) , A. Telek b) and T. Bíró b)
Hair follicle (HF) is an appendage organ
of the skin which is of importance to the sur-
vival of mammals and still maintains signifi-
cance for the human race - not just biologically,
but also through cosmetic and commercial con-
siderations. However data on the composition
of hair follicles are scarce and mostly limited
to the hair shaft. In addition, to the best of
our knowledge, no data are available concern-
ing the distribution of elements in human hair
follicle with various growth and cycling phases.
In this study [1] we provided detailed
quantitative elemental distribution of organ-
cultured hair follicle in anagen and catagen
growth phases using ion microscopy in order
to reach a better understanding of the func-
tion, development, and cyclic activity of the
hair follicle. The microprobe analysis was car-
ried out at the scanning ion microprobe fa-
cilities at the ATOMKI Debrecen, and at the
Jožef Stefan Institute, Ljubljana, Slovenia, us-
ing combined STIM and PIXE ion beam ana-
lytical techniques.
Human anagen hair follicles were isolated
from skin obtained from females undergoing
face-lift surgery. Cultured anagen HFs were
treated by either vehicle or by 10 µM capsaicin
for 5 days.
Elemental distributions and absolute con-
centrations were determined along 5 capsaicin
treated (catagen), and 4 control (anagen) hair
follicles. The investigated length varied be-
tween 1.5 and 2 mm. Average elemental con-
centration values of the whole sample and the
different morphological parts were also deter-
mined.
Concentrations for most of the elements
were found to be the same in the correspond-
ing parts of the anagen and the catagen hair
follicles. However, significant differences were
observed in the Ca concentration between the
anagen and catagen HFs. With respect to the
63
distribution of Ca, in anagen (control) HFs,
the following concentrations were measured
(given in µg/g dry weight): dermal papilla,
∼500; matrix of the bulb, 1000-1500; outer/
inner root sheath keratinocyte layers, 1000-
2000; hair shaft, 1000-2000. The induction
of catagen transformation essentially did not
change the Ca concentrations in the dermal
papilla, bulb matrix regions nor in the hair
shaft (1000-2000 in all parts). In contrast, we
observed a remarkable increase in the outer/
inner root sheath keratinocyte layers up to
4000-8000 µg/g Ca concentration.
In capsaicin-treated catagen HFs, the Ca
concentration was increased mostly in those
layers which possess a significant expression
of TRPV1, the receptor for capsaicin. Since
TRPV1 functions as a Ca-permeable channel,
the elevated Ca in the TRPV1-expressing lay-
ers suggest that the activation of TRPV1 by
capsaicin resulted in a prolonged elevation of
intracellular Ca-concentration which, in turn,
led to the inhibition of proliferation of HF ker-
atinocytes as well as the induction of HF apop-
tosis. Moreover, our findings also show that ion
microscopy may serve as a fine tool to detect
changes in elemental distribution related to the
human hair-cycle.
Acknowledgements
This work was supported by the
Hungarian-Slovenian Intergovernmental S & T
Cooperation programme (contract no. OMFB-
00427/2006) and the Hungarian Research Fund
(contract no. K063153).
a) Jožef Stefan Institute, Ljubljana, Slovenia
b) Department of Physiology and Cell Physiology Re-
search Group of the H. A. S., University of De-
brecen, Medical and Health Science Center, Re-
search Center for Molecular Medicine.
[1] Zs. Kertész et al., Nuclear Instruments and Meth-
ods B, in press, ref.: NIMB 54339