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Biomimetic Based Applications Part 3 ppt

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Homogeneous and Heterogeneous Free-Based Porphyrins Incorporated to Silica Gel as Fluorescent Materials and Visible Light Catalysts Mimic Monooxygenases 71 89( +7,( @#8+83"+,2( @8#@7*#$3( $3( +7,( &*&+,:0( ;7$=7( $&( -38;3( +8( 7"B,( +7,( ,37"3=,2( 2,"=+$B"+$83(89(+7,(,E=$+,2(&+"+,(F\7$#B83*(,+("<C0(4HHHIC(Z3(9"=+0($+(;"&(,&+"><$&7,2(>"&,2(83( +7,(">&8#@+$83(&@,=+#"(89(@8#@7*#$3&(#,=8#2,2(>,98#,("32("9+,#(@78+8="+"<*&$&( (Fig 5)(+7"+( @8#@7*#$3($3(+7,(&*&+,:(;$+7("(<8;(=83=,3+#"+$83(89(<$:83,3,(,E$&+&($3("(@#8+83"+,2(98#:(89( ( O[nm] 200 250 300 350 400 450 500 550 600 650 700 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 A limonene 1% 418 nm 445 nm 200 250 300 350 400 450 500 550 600 650 700 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 limonene 90% 418 nm A O[nm] 500 550 600 650 700 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 500 550 600 650 700 0.00 0.02 0.04 0.06 0.08 Soret band Q-band 15 x Soret band Q-band 20 x 670 nm H 2 TPP 10 -4 mol/dm 3 H 2 TPP 10 -4 mol/dm 3 515 nm 550 nm 590 nm 648 nm 515 nm 550 nm 590 nm 648 nm ( 6$?C(QC(K>&8#@+$83(&@,=+#"(89(+7,(J 4 )OON<$:83,3,(&*&+,:(F"+(+;8(2$99,#,3+(&%>&+#"+,( =83=,3+#"+$83&I($3(=7<8#898#:](>,98#,(@78+8#,"=+$83(F><"=-(&8<$2(<$3,I0("9+,#(Mj(7(F#,2(2"&7( <$3,I("32(.4j(7(F?#,,3(2"&7(<$3,I(,E@8&$+$83(+8(+7,(&%3<$?7+(F)#*+,-("+("<C0(4HHSIC( Biomimetic Based Applications 72 2$="+$83(J P )OO 4m C(K&("(=7"#"=+,#$&+$=(kN>"32(;"&(83<*(8>&,#B,2(98#(9#,,N>"&,(J 4 )OO(FQHHN jQH(3:I("32(2$="+$83(J P )OO 4m( FjSH(3:I0(+7$&(:,"3&(+7"+(+7,(="+"<*+$=(&*&+,:($&(>"&,2(1%&+(83( @78+8,E=$+,2(@8#@7*#$3,("32(+7,(:,+"<(=83+":$3"+$83($&(,E=<%2,2C()7,(@8#@7*#$3(&@,=+#"( ;$+7( "( 7$?7( RHs( =83=,3+#"+$83( 89( <$:83,3,( 2%#$3?( @78+8,E=$+"+$83( &78;,2( +7"+0( 3,$+7,#( U8#,+(38#(k(>"32&(;,#,(&7$9+,20("32(83<*(+7,$#($3+,3&$+*(;"&(&<$?7+<*(<8;,#("9+,#($##"2$"+$83( +7"3(>,98#,($+0(;7$=7( 28,&( 38+($32$="+,( +7"+( +7,( ="+"<*&+($&( #,"2$<*(2,=8:@8&,2( %32,#( +7,( "@@<$,2( 8E$2$'$3?( =832$+$83&C( Z3( +7$&( =83+,E+0($+($&(;8#+7(+"-$3?($3+8("==8%3+(+7"+(+7,( @#,&,3=,( 89( "( <"#?,( ,E=,&&( 89( #,"2$<*( 8E$2$',2(&%>&+#"+,&(;$<<(@#8B$2,(-$3,+$=(@#8+,=+$83( "?"$3&+(8E$2"+$B,(2,&+#%=+$83(89(+7,(>$8:$:,+$=(="+"<*&+&(FU%&<$=-0(.RRRIC( )7,("%+78#&(=83=<%2,2(+7"+(&%=7(&@,=+#"<(=7"3?,&("#,(+7,(,B$2,3=,(98#(+7,(,E$&+,3=,(89(+;8( 2$99,#,3+(:,=7"3$&:&(89(:838+,#@,3,&(@78+88E$2"+$83(>*(J 4 )OO0(+8(+7,(,E+,3+(,E+#,:,<*( 2,@,32,3+( 83( +7,( &%>&+#"+,( =83=,3+#"+$83C(68#(+7,(&*&+,:&(;$+7("(<8;,#(&%>&+#"+,( =83=,3+#"+$830( "(@#8+83( "==,@+$3?( :,=7"3$&:($&(:8#,($:@8#+"3+0(;7,#,"&($3(+7,(&*&+,:&( ;$+7("(<"#?,#(":8%3+(89(:838+,#@,3,0(J 4 )OO(#"+7,#(@<"*&("(#8<,(89("(@78+8&,3&$+$',#("32( 8E$2"+$B,(+#"3&98#:"+$83($&(:8&+(@#8>"><*(>"&,2(83("(9#,,(#"2$="<(=7"$3(@"+7;"*($3$+$"+,2(>*( @78+8,E=$+,2(@8#@7*#$3(@#82%=$3?(&$3?<,+(8E*?,3C(U$3?<,+(8E*?,3($&("(@8;,#9%<(,<,=+#8@7$<,0( &8( +7,( #,"=+$83( :"*( @#8=,,2( 1%&+( "&( ;,<<( >*(,<,=+#83(+#"3&9,#(9#8:( +7,( ,<,=+#83( #$=7( :838+,#@,3,&(+8($+C()7,(=8::83(:,=7"3$&:(89("=+$83(89(+7,(&,3&$+$',#($&(#"+7,#(=8:@<,EC( )7,(">&8#>,2(<$?7+(@#8:8+,&(+7,(,E=$+,2(&+"+,(89(+7,(@8#@7*#$3(="+"<*&+C()7,(&$3?<,+N,E=$+,2( &+"+,(F= . 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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( &+"=- $3? (28,& (38 +("<<8;(" ;3( 8@+$:"<( $3+ ,#"=+$ 83( 89(+7,(@ $3, 3,(;$+7(:"=#8=*=<,&( FO"8<,&&,(,+("<C0(4HH4IC( Biomimetic Based Applications 90 83= ,3+ #"+$ 83( 89(@#82%=+&(F?YeI( )% #38 B,# (3% :>,#( 83= ,3+ #"+ $ 83( 89( J 4 WXO( $3( &8<(F!I( @ $38 ="#B 83, '&%)0N @ $38 ="#B,8< :*#+ ,38 <. $&( =8:@"#,2(;$+7(+7"+( $3( ?,<C((U7$9+(89(+7,(U8#,+(>" ;32 ( $3( 2$#,=+$ 83( 89(&78#+,#(;"B,< ,3? +7&(;"&( 8>&,#B,2(" ;32 (,E@<" $3, 2(>*(+7,(2$:,#$'"+$ 83( 89(@8#@7*# $3( " ;32 ( $3+ ,#"=+$ 83( 89(@8#7*# $3, (;$+7( +7,(&8<$2(&%#9"=,C(U7$9+(89(+7,(9<%#,&= ,3= ,(>" ;32 (9#8:(jQH(+8(jjQ (3: (;"&("<&8(98 %32 (;$+7(+7,( $3= #,"&,( $3( +7,("2&8#>,2()!O*O(":8 %3+ &C()7,(<%: $3, &= ,3= ,( $3+ ,3& amp;$+*(B"#$,2(2,@ ,32 $3? ( 83( +7,( "2&8#>,2( ":8 %3+ &( " ;32 ( +7,( B"#$"+$ 83( ;"&( 38 +( &$:@<,C( W==%# ,3= ,( 89( <%: $3, &= ,3= ,( A% ,3= 7 $3? ( $3= <%2 $3? (&,<9NA% ,3= 7 $3? (;"&(&%??,&+,2C( f%(

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