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(J 4 ())!,OOY\83(K(.V.("&&8=$"+,(F2"&7,2(<$3,I(,E=$+,2("+(4jH(3:(F>I](&#$&+./4'1+)*?1':* $#&(1001+)*,&+(*V$'14%2*3%'#&1%208*4+$7&16:'*EFFWC* ( ( 6$?C( C(\7,:$="<(&+#%=+%#,&(89(@8#@7*#$3&(,3="@&%<"+,2($3(&$<$="(?,<(&78;$3?(>$8:$:,+$=( "=+$B$+*($3(@78+88E*?,3"+$83(89(:838+,#@,3,&C( J:ONZf J 4 WXO N NH N NH CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 N N NH NH CH 3 CH 3 O O OHOH CH 3 CH 3 CH 3 OH OH CH 3 Biomimetic Based Applications 80 )#*+,-(,+("<C(F4HHRI(&+%2$,2(+7,(9<%8#,&=,3+("32(>$8="+"<*+$="<(@#8@,#+$,&(89(;"+,#(&8<%><,("32( $3&8<%><,( @#8@7*#$3&( $3+,#="<"+,2($3(+7,(&$<$="(&8<N?,<(:"+#$EC )7,( $3&@,=+$83( 89( ghNh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k(>"32(#,?$83(+7,(3,;0(B,#*($3+,3&$B,(>"32("+( jQQ(3:(;"&(8>&,#B,2( "32( $+&(,E$&+,3=,(;"&(@#8>"><*(+7,(#,&%<+(89(@8#@7*#$3(@#8+83"+$83( ;$+7(=83&,A%,3+(2$="+$83(98#:"+$83C(Z3(+7,(,:$&&$83(&@,=+#%:(89(J 4 )OO(+7,(9<%8#,&=,3=,(89( &8<("32(+7,(2#$,2(?,<(;"&(,B$2,3+<*(<,&&($3+,3&$B,(+7"3(<%:$3,&=,3=,($3(+7,(c!UW(&8<%+$83( "&("(#,&%<+(89(@8#@7*#$3("??<8:,#"+$83C()7,(&7$9+(89(+7,(<%:$3,&=,3=,(:"E$:%:(9#8:(jQH(+8( jjS(3:0(;7,3(&8<(;"&(=8:@"#,2(;$+7(+7,(2#$,2(&":@<,0(=839$#:,2(+7,(2$="+$83(,E$&+,3=,($3( +7,(2#$,2(?,<C( ( λ [nm] 300 350 400 450 500 550 600 650 700 A 0,0 0,5 1,0 1,5 2,0 2,5 Soret 391 nm 0,00 0,02 0,04 0,06 0,08 0,10 0,12 0,14 0,16 0,18 0 1x10 -6 2x10 -6 4x10 -6 6x10 -6 8x10 -6 1x10 -5 1.2x10 -5 1.4x10 -5 1.6x10 -5 1.8x10 -5 2x10 -5 2.2x10 -5 Q x10 505 536 568 ~630 C M x10 6 [mol/dm 3 ] 0510152025 A 0,0 0,5 1,0 1,5 2,0 2,5 λ = 391 nm HmP IX/SiO 2 , one week after gelation λ [nm] 300 350 400 450 500 550 600 650 700 A 0,00 0,05 0,10 0,15 0,20 0,25 Soret 389 nm 0,000 0,005 0,010 0,015 0,020 0,025 0 mol/dm 3 1x10 -6 2x10 -6 4x10 -6 6x10 -6 8x10 -6 1x10 -5 1.2x10 -5 1.4x10 -5 1.6x10 -5 1.8x10 -5 2x10 -5 Q x10 ~500 ~530 ~557 ~600 C M x10 6 mol/dm 3 02468101214161820 A 0,00 0,05 0,10 0,15 0,20 0,25 λ = 389 nm H 2 OEP/SiO 2 , one week after gelation ( 6$?C(.4C(ghNh$&(">&8#@+$83((&@,=+#"(89(J:O(Zf("32((WXO($3+,#="<"+,2($3(U$W 4 ("<=8?,<(F+7,( 3%:>,#&(2,38+,(+7,($3$+$"<(=83=,3+#"+$83&(89(@8#@7*#$3&($3(&$<$="(&8<IC( [...]... 408 407 39 9 39 9 39 9 39 9 1 ,0 0 ,8 0 ,6 Q -5 -5 -5 -5 552 - 551 0 ,4 5 93 - 592 0 ,2 0 ,0 30 0 35 0 400 450 500 550 600 650 700 λ [n m ] H2OEP/SiO 2 xerogel, 7 months after gelatio n 2 ,2 A 2 ,0 0 1 x 1 0 -6 2 x 1 0 -6 4 x 1 0 -6 6 x 1 0 -6 8 x 1 0 -6 1 x 1 0 -5 1 2 x 1 0 1 4 x 1 0 1 6 x 1 0 400 nm 1 ,8 39 8 1 ,6 39 9 1 ,4 Q S o re t 1 ,2 39 9 1 ,0 -5 -5 -5 0 ,8 547 546 0 ,6 39 8 0 ,4 589 0 ,2 0 ,0 30 0 35 0 400... 0.125 1.8× 10-5 0.797 0.1 23 0.068 2× 10-5 1 .3 0.219 0.198 Turnover number pinocarvone 2 285.7 2 717.1 3 537 .4 4225.7 2 514.2 2 212.8 1 34 3.0 1 279.8 1 575.6 1 132 .1 1 666.2 transmyrtenol pinocarveol 615 .3 579.2 588.0 38 3.9 670.1 478.0 408.4 277.7 34 5.6 260.5 226.9 124.5 211.2 125 .3 284.2 199.7 170.5 110.8 2 73. 9 250.6 Table 1 Effect of initial concentration of octaethylporphyrin in silica on its biocatalytic... 3, 261-2 73 Lisowski, J.; Sessler, J.L & Mody, T.D (1995) 13C and 31 P NMR study of paramagnetic lanthanide (III) texaphyrins Inorganic Chemistry, Vol 34 (17), 433 6– 434 2 Maldotti, A.; Bartocci, C.; Varani, G.; Molinari, A.; Battioni, P & Mansuy, D (1996) Oxidation of cyclohexane by molecular oxygen photoassisted by mesotetrarylporphyrin iron(III)-hydroxo complexes Inorganic Chemistry, Vol 35 , 11261 131 ... clean technology, green chemistry, and sustainable development Annual Review of Materials Research, Vol 35 , 31 5 -35 0 Traylor, T & Tsuchiya, S (1987) Perhalogenated tetraphenylhemins: stable catalysts of high turnover catalytic hydroxylations Inorganic Chemistry, 26(8), 133 8– 133 9 104 Biomimetic Based Applications Trytek, M., & Fiedurek, J (2002) Biotransformation of d-limonene to carvone by means of glucose... 40(1-2), 2 53- 254 Maraval, V.; Ancel, J & Meunier, B (2002) Manganese(III) porphyrin catalysts for the oxidation of terpene derivatives: a comparative study Journal of Catalysis, Vol 206(2), 34 9 -35 7 100 Biomimetic Based Applications Margaros, I.; Montagnon, T.; Tofi, M.; Pavlakos, E & Vassilikogiannakis G (2006) The power of singlet oxygen chemistry in biomimetic syntheses Tetrahedron, Vol 62, 530 8– 531 7... Intensity, a.u 40 ~400 nm l 35 594 nm 30 25 3 1x10 -6 mol/dm -6 2x10 4x10 -6 6x10 -6 8x10 -6 1x10 -5 -5 1.2x10 1.4x10 -5 1.6x10 -5 1.8x10 -5 2x10 -5 549 nm ~34 5 nm ~425 nm 20 15 10 5 0 35 0 400 450 500 550 600 650 λ [nm] H2OEP/SiO 2 80 l 70 ~35 5 nm 3 1x10 -6 mol/dm 2x10 -6 4x10 -6 6x10 -6 8x10 -6 1x10 -5 1.2x10 -5 1.4x10 -5 1.6x10 -5 545 nm ~400 nm 60 50 ~412 nm 590 nm 40 30 20 10 0 35 0 400 450 500 550 600... (2000) Grafting of cobalt porphyrins in sol-gel matrices: application to the detection of amines Sensors and Actuators B, Vol 62, 136 -142 DeRosa, M & Crutchley, R (2002) Photosensitized singlet oxygen and its applications Coordination Chemistry Reviews, Vol 233 - 234 , 35 1 -37 1 Doro, F.G.; Smith, J.R ; Ferreira, A.G & Assis, M D (2000) Oxidation of alkanes and alkenes by iodosylbenzene and hydrogen peroxide... 90 Biomimetic Based Applications Concentrat Concentration of products (g/L) ion of H2OEP in transpinocarvone myrtenol sol (M) pinocarveol 1× 10-6 0.087 0.024 2× 10-6 0.206 0.045 4× 10-6 0.546 0.0 93 0.06 6× 10-6 0.96 0.156 0.111 8× 10-6 0.769 0.128 0.086 1× 10-5 0.856 0. 137 0.102 1.2× 10-5 0.618 0.107 0.058 1.4× 10-5 0.686 0.116 0.068 1.6× 10-5 0.974 0.180 0.125 1.8× 10-5 0.797 0.1 23 0.068 2× 10-5 1 .3. .. 650 nm) 84 Biomimetic Based Applications Fig 16 The emission spectra comparison of HmP IX, H2OEP in alco- and xerogel (excitation wavelength 39 0 nm) Textural characteristics of silica xerogel based on N2 adsorption revealed the microporous character of adsorbent, however, apart from the micro-, the meso- and macropores were present in the silica structure with the pore size diameter: 17 -30 00 Å; therefore... Molecular Catalysis A: Chemical, Vol 233 , 73- 81 Mukherjee, M & Ray, A (2007) Biomimetic oxidation of l-arginine with hydrogen peroxide catalyzed by the resin-supported iron (III) porphyrin Journal of Molecular Catalysis A: Chemical, Vol 266(1-2), 207-214 Murahashi, S-I & Komiya, N (1998) New types of catalytic oxidations in organic synthesis Catalysis Today, Vol 41(4), 33 9 -34 9 Murata, S.; Hata, H.; Kimura, . J 4 WXO N NH N NH CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 N N NH NH CH 3 CH 3 O O OHOH CH 3 CH 3 CH 3 OH OH CH 3 Biomimetic Based Applications 80 )#*+,-(,+("<C(F4HHRI(&+%2$,2(+7,(9<%8#,&= ,3+ (" ;32 (>$8="+"<*+$="<(@#8@,#+$,&(89(;"+,#(&8<%><,(" ;32 ( $3& amp;8<%><,(. 89( ="+"<*&+&( $3( +7,(&$<$="(:,2$%:C()7$&($&( $3( " ;3( "?#,,: ,3+ (;$+7(+7,(:8#,(? ,3, #"<(#%<,(+7"+(+7,( 98#:"+$ 83( 89("(2$="+$ 83( " ;32 (2$:,#&(8#(7$?7,#(8#2,#("??#,?"+,&(2,=#,"&,&(@78+8"=+$B$+*(89(+7,( @78+8& ,3& amp;$+$',#&(FG,#2,&(,+("<C0(.RRS](Z<$,B(,+("<C0(4HHH]()" ;3$ ,<$" ;3( ,+("<C0(4HH.I("&(+7,(@#,& ,3= ,( 89(@8#@7*# $3( &+"=- $3? 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