untitled ISSN 215 Synthes and thei Raquel Eu Octavio O 1 Instituto Polité México 2 Instituto Mexic México 3 Benemérita Un México 4 Centro de Nano D.F, México * Corresponding Azcapotzalco, C Tel.: +52.55.572 ARTICLE IN DOI: 10.5155/e Received: 28 Oc Received in rev Accepted: 05 De Published onlin Printed: 31 Mar KEYWORDS Chelating Porphyrin Metal species Metal complex PAMAM sendrim Microwave synt 1. Introduct Often, th used as pr macromolecu fundamental matter of fac subunits are groups. Porp ently, as com Cu(II), etc. [ important pl important m undoubtedly and Lindsey been carried 53‐2249 (Print) sis of porp ir metal c unice Hernan livares‐Xom écnico Nacional, Ce cano del Petróleo, D niversidad Autónom ociencias y Micro y g author at: Institu CP 02250, México D. 296000. Fax: +52.55 FORMATION eurjchem.7.1.49‐55 ctober 2015 vised form: 01 Dece ecember 2015 ne: 31 March 2016 rch 2016 S mers thesis tion he simplest he rimary‐block‐bu ules [1]. As it l piece of the b ct, porphyrins a e linked via the phyrins are wi mplexes with m [2‐3]. The che lace in the hist method for t y the Rothemun methods. In su d out using corr / ISSN 2153‐225 ht Europ phyrins as chelating p ndez‐Ramir metl 3 and Lu entro de Investigaci Dirección de Investi ma de Puebla, Facu y Nanotecnologías, to Politécnico Naci .F., México. 5.57296000. E‐mai 5.1352 ember 2015 eterocyclic com uilding units is well known, basic structure are compounds e α‐positions th idely distribute metallic cation mistry of porp ory of organic the synthesis nd synthesis; o ummary, porph osive, high boil European Journ Europ 57 (Online)  20 ttp://dx.doi.org pean Jo Journal web s precurs propertie rez 1, Irina V uis Lartundo ión e Innovación Te igación y Posgrado ltad de Ingeniería Q Luis Enrique Erro S ional, Centro de Inv l address: irinalijan ABSTRACT Novel meso‐p centers to p porphyrins w porphyrin‐PA molecular w spectrometry form Ag0 spe chemical redu Cite this: Eur. mpounds have for most com , pyrrole (azole of porphyrins s where four py hrough four me ed in nature, f s like Fe(II), M phyrins occupi chemistry. The of porphyri others are the hyrin syntheses ling point solve al of Chemistry 7 pean Journal of C 016 Atlanta Pub /10.5155/eurjch ournal bpage: www. ors to PA es ictorovna Li o‐Rojas 4 ecnológica, Cerrada o, Eje Central Lázar Química, Av. San Cl S/N, U. Profesional vestigación e Innov nova@yahoo.com.m porphyrins wer polyamide amin were characteri AMAM dendrime eight of the p y. These porphyr ecies and doped uction of the met . J. Chem. 2016, been mplex e) is a . As a yrrole ethine frequ‐ Mg(II), ies an e most ns is Adler s have ents or larg [4‐5 opt con con syn usin reac the sam mat the beg rese pro 7 (1) (2016) 49‐ Chemistry lishing House LL hem.7.1.49‐55.1 of Che .eurjchem.co AMAM den ijanova 1,*, N a Cecati S/N, Colon ro Cárdenas No. 152 laudio y 18 Sur, Col l Adolfo López Mate vación Tecnológica, mx (I.V. Lijanova). re synthesized v ne (PAMAM) d ized by UV‐Vis ers were charac prepared dendr rin‐core‐PAMAM d nylon membr tal cation. 7(1), 49‐55 ge volumes of a 5]. The microwav tion because it c nditions with yi nvectional heat nthesis of tetra ng silica gel as ct [6‐7]. When temperature mple is heated terials is prom obtained benef The introduct gan mainly as emblance of oteins [10]. Ove ‐55 LC ‐ All rights re 1352 emistry m ndrimers Natalya Vict nia Santa Catarina, 2, Col. San Bartolo l. San Manuel, Ciud eos, Gustavo A. Mad Cerrada Cecati S/N via microwave dendrimers. Th , 1H and 13C N cterized by 1H rimers were c M‐modified dend ranes, using the a halogenated s ve assisted synt can be carried o ields that are b ting. It has be aphenyl porphy a solid suppo microwaves a is increased d, and the rea oted, where a fits [8‐9]. ion of porphyr core entities these macrost r the years, por served ‐ Printed y orovna Likh Azcapotzalco, CP 0 Atepehuacan, Méxi dad Universitaria, P dero, C.P. 07738 Ciu N, Colonia Santa Ca assistance and he molecular s NMR spectrosco and 13C NMR s onfirmed by M rimers were use e XPS techniqu olvent containi hesis of porphy out under no‐so better than tho en reported th yrins by micro rt, pyrrole and are used as an rapidly becau action between short reaction rins into dendr s due to the tructures to n rphyrin macroc d in the USA hanova 2, 02250, México D.F., ico D.F., 07730, Puebla, 72570, udad de México, atarina, implemented a tructures of th opy. In additio spectroscopy. Th MALDI‐TOF ma ed as templates e to confirm th ing Lewis acids yrins is a viable olvent‐reaction se obtained by hat during the owave heating, d benzaldehyde energy source, use the entire n the starting time is one of ritic structures morphological natural hemo‐ cycles have also , as he on, he ss to he s e n y e , e , e g f s l ‐ o 50 Ramírez et al. / European Journal of Chemistry 7 (1) (2016) 49‐55 been introduced as surface groups either within the dendritic branches or spread throughout the entire molecule architecture [11‐12]. Porphyrin dendrimers are hybrid molecules to be used in biomimetics, artificial photosynthesis, catalysis with biomedical applications and optoelectronics [13]. Recent studies include the appendage of metal redox centers, which are important for some regiospecific catalytic properties; on the other hand, the incorporation of porphyrins into dendrimers has shown an unusual photophysical and electrochemical redox behavior [14‐15]. The porphyrin‐core dendrimers have been studied because the terminal substituent groups on the photoactive core can modulate their physicochemical properties. This fact has been extensively studied for a number of different applica‐ tions such as catalysts, organic solar cells, photoelectron‐ chemical devices, light‐emitting diodes, and photodynamic therapy [16]. Different classes of dendrimers bearing 8 and 32 fluorene donor groups have been synthetized, and UV‐vis spectra have confirmed that the individual properties of donor and acceptor moieties are preserved; on the other hand, the efficient energy transfer shown by these dendrimers has been evidenced by fluorescence spectroscopy studies [17]. PAMAM dendrimers have been functionalized using a resorcinarene core, and it has been found that by this functionalization, it is possible to obtain nickel and copper retentions of 35 and 70 %, respectively, in neutral‐pH aqueous solutions at room temperature. In addition, a study of trialkylamine compounds has shown that the retention of metal cations such as nickel, copper, lead, zinc, and cobalt from an aqueous solution with an initial concentration of 25 ppm at room temperature and neutral pH can be highly efficient: for Ni (II), the efficiency was up to 96.00 %; for Pb (II), it ranged from 93.00 to 99.00 %; and for Cu (II), it almost reached 100 % [18‐19]. The use of dendrimers as templates for the synthesis of metal particles is a promising methodology with applica‐ tions in either the catalysis field or as chemical sensors due to the globular and controlled structure of these molecules [20‐ 22]. PAMAM dendrimers are the most widely used compounds for these purposes because their structure and composition are uniform, so the obtained metallic particles are encapsulated inside the dendrimer and kept stable due to a steric impediment without being passivated [23]. The method for obtaining metal particles encapsulated in dendrimers consists of two steps: the addition of metal cations to the dendrimer structure and the chemical reduction of these cations to obtain neutral metal atoms. The synthesis of Au, Pd, Pt and Ag particles has been reported for this method [24‐25]. In this sense, metallic silver particles are of great interest due to their good conductivity, chemical stability and catalytic and antibacterial activity in addition to other biomedical applica‐ tions such as antivirals and fungicides [26‐27]; furthermore, silver particles are important catalysts in the production of major industrial chemicals because these metal atoms are not affected by the reaction, and they are almost completely recovered after being used [28]. 2. Experimental 2.1. Instrumentation Solvents and reagents were purchased from Aldrich and used without further purification. Infrared spectra were recorded on a Nicolet FT‐IR Magna 700 spectrometer. 1H (300 MHz) and 13C NMR (75 MHz) spectra were recorded on a JEOL Eclipse‐300 equipment in CDCl3, and chemical shifts are expressed in ppm relative to tetramethylsilane used as internal standard. Mass spectra were recorded on a Micromass TofSpec (MALDI‐TOF) using 2,5‐dihydroxybenzoic acid (DHB) as matrix. The X‐ray photoelectron spectroscopy allowed to perform a surface‐sensitive‐quantitative‐spectroscopic and elemental analysis. The same reactions were performed by a microwave device Monowave 300 Anton PARR. 2.2. Synthesis 2.2.1. Tetraphenyl porphyrin with four active points (3a and 4a) Compound 3a: 2‐Methoxy benzaldehyde (0.6856 g, 5 mmol) was added to pyrrole (0.3354 g, 5 mmol) at 70 °C, using a microwave reactor Monowave 300 with constant stirring for 2 h. The presence of porphyrin (3a) was corroborated by means of thin layer chromatography and it was continued by column chromatography purification. An intense purple powder was obtained (Scheme 1). Color: Deep purple. Yield: 10%. FT‐IR (KBr, , cm‐1): 3330, 1603, 1501, 1240, 1170, 998, 750. UV/Vis (CH3OH, λmax, nm): 230, 420, 525, 550, 600, 650. 1H NMR (300 MHz, DMSO‐d6, δ, ppm): ‐2.82 (s, 2H, pyrrole int.), 3.83 (s, 12H, OCH3), 6.94‐7.27 (m, 8H, Ar‐H), 8.01 (br, 8H, Ar‐H), 8.34 (br, 8H, pyrrole). 13C NMR (75 MHz, DMSO‐d6, δ, ppm): 56.2 (O‐CH3), 99.13 (methine), 111.4 (Ar), 119.9 (Ar), 120.7 (pyrrole), 120.9 (Ar), 128.9 (Ar), 142.1 (pyrrole), 156.65 (Ar‐porphyrin), 161.1 (pyrrole). MALDI‐TOF (m/z): 734. Anal. calcd. for C48H38N4O4: C, 78.45; H, 5.21; N, 7.62. Found: C, 77.29; H, 5.67; N, 7.47%. Compound 4a: Afterwards, porphyrin 3a (0.1 g, 0.136 mmol) was added to 50 mL of dichloromethane at 100 °C, obtaining a homogeneous solution. Later, it was cooled at 0 °C to add BBr3 (0.1363 g, 0.5443 mmol). The reaction was kept under constant stirring for 24 h. The product was dried in a rotary evaporator and later, it was precipitated using a dichloromethane‐hexane solution (1:1, v:v), obtaining the unprotected porphyrin 4a (Scheme 1). Color: Deep purple. Yield: 97%. UV/Vis (CH3OH, λmax, nm): 200, 230, 420, 525, 550, 600, 650. FT‐IR (KBr, , cm‐1): 3580, 1603, 1501, 1240, 1070, 998, 750. 1H NMR (300 MHz, CDCl3, δ, ppm): ‐2.82 (s, 2H, pyrrole int.), 5.35 (s, 4H, O‐CH3), 6.94‐7.27 (m, 8H, Ar), 8.01 (br, 8H, Ar), 8.34 (a, 8H, pyrrole). 13C NMR (75 MHz, CDCl3, δ, ppm): 99.13 (methine), 111.4 (Ar), 119.9 (Ar), 120.7 (pyrrole), 120.9 (Ar), 128.9 (Ar), 142.1 (pyrrole), 156.65 (Ar‐porphyrin), 161.1 (pyrrole). MALDI‐TOF (m/z): 678.23. Anal. calcd. for C44H30N4O4: C, 77.86; H, 4.46; N, 8.25. Found: C, 77.63; H, 5.11; N, 8.29%. 2.2.2. Tetraphenyl porphyrin with twelve active points (3b and 4b) 2,4,6‐Trimethoxy benzaldehyde (0.1 g, 5 mmol) and trifluoroacetic acid (0.149 g, 1.3067 mmol) were added to 50 mL of dichloromethane at 70 °C and constant stirring. Afterwards, pyrrole (0.3354 g, 5 mmol) was added and the reaction continued at room temperature for 72 h. Finally, 2,3‐ dichloro‐5,6‐dicyano‐1,4‐benzoquinone (1.135 g, 5 mmol) was added at room temperature and the reaction was carried out for 24 h more. The presence of porphyrin was corroborated by thin layer chromatography and it was purified by column chromatography (Scheme 1). Compound 3b: Color: Reddish powder. Yield: 13 %. UV/Vis (CH3OH, λmax, nm): 220, 301, 418, 518, 545, 589, 657. FT‐IR (KBr, , cm‐1): 3118, 1673, 1200, 1090, 820, 730. 1H NMR (300 MHz, CDCl3, δ, ppm): ‐2.84 (s, 2H, pyrrole int.), 3.68 (s, 36H, O‐ CH3), 7.15‐7.24 (m, 8H, Ar), 8.01 (br, 4H, Ar), 8.17 (br, 4H, pyrrole). 13C NMR (75 MHz, CDCl3, δ, ppm): 56.2 (O‐CH3), 90.8 (Ar), 91.1 (Ar), 102.6 (Ar‐ring), 103.1 (methine), 122.7 (pyrrole), 132.1 (pyrrole), 142.33 (pyrrole), 158.9 (Ar), 159.6 (Ar), 162.41 (pyrrole). MALDI‐TOF (m/z): 974.37. Anal. calcd. for C56H54N4O12: C, 68.98; H, 5.58; N, 5.75. Found: C, 69.11; H, 5.73; N, 5.81%. Compound 4b: Porphyrin 3b (0.1 g, 0.1025 mmol) was added to 50 mL of dichloromethane at 100 °C until obtaining a homogenous solution. Ramírez et al. / European Journal of Chemistry 7 (1) (2016) 49‐55 51 Scheme 1 Later, it was cooled at 0 °C to add BBr3 (0.3082 g, 1.2306 mmol). The reaction was kept under constant stirring for 24 h. The product was dried in a rotary evaporator and later precipitated with a dichloromethane‐hexane solution, obtaining the unprotected porphyrin‐2, 4b (Scheme 1). Color: Purple. Yield: 91%. UV/Vis (CH3OH, λmax, nm): 220, 301, 418, 518, 545, 589, 657. FT‐IR (KBr, , cm‐1): 3638, 1673, 1200, 1010, 820, 730. 1H NMR (300 MHz, CDCl3, δ, ppm): ‐2.84 (s, 2H, pyrrole int.), 5.89 (s, 12H, OH), 7.15‐7.24 (m, 8H, Ar), 8.01 (br, 4H, Ar), 8.17 (br, 4H, pyrrole). 13C NMR (75 MHz, CDCl3, δ, ppm): 91.04 (Ar), 91.78 (Ar), 102.6 (Ar‐ring), 103.1 (methine), 122.7 (pyrrole), 132.1 (pyrrole), 142.33 (pyrrole), 158.9 (Ar), 159.6 (Ar), 162.41 (pyrrole). MALDI‐TOF (m/z): 806.19. Anal. calcd. for C44H30N4O12: C, 65.51; H, 3.75; N, 6.94. Found: C, 65.23; H, 4.13; N, 7.04%. 2.2.3. Synthesis of 0.5 generation dendrimers (6a, 6b) Separately, cesium carbonate (0.1920 g, 0.5893 mmol; 0.4846 g, 1.4874 mmol) and unprotected porphyrins 4a, 4b (0.1 g, 0.1473 mmol; 0.1 g, 0.1239 mmol) were added to 70 mL of acetone at 110 °C for 1 h. Finally, methyl bromo acetate (0.9 g, 0.5893 mmol; 0.2275 g, 1.4874 mmol) was added. The reaction was kept for 11 h more under constant stirring at the same temperature. The presence of the product was corroborated by thin layer chromatography and it was purified by filtering the solution in order to eliminate the cesium carbonate and later drying it in a rotary evaporator, finishing with a precipitation using a dichloromethane‐hexane solution (1:1, v:v), obtaining the 0.5 generation dendrimer 6a, 6b as an intense purple powder (Scheme 2). Compound 6a: Color: Metallic purple. Yield: 90%. UV/Vis (CH3OH, λmax, nm): 220, 255, 421, 522, 568, 597, 679. FT‐IR (KBr, , cm‐1): 3448, 3314, 2986, 2851, 1754, 1603, 1509, 1223, 1168. 1H NMR (300 MHz, CD3OD, δ, ppm): ‐2.88 (s, 2H, pyrrole int.), 3.94 (s, 12H, O‐CH3), 4.91 (s, 8H, CH2‐C=O) 7.24‐ 7.28 (m, 8H, Ar), 8.09‐8.10 (m, 8H, Ar), 8.12 (s, 8H, pyrrole). 13C NMR (75 MHz, CD3OD, δ, ppm): 51.9 (O‐CH3), 64.89 (O‐ C*H2‐C=O), 99.3 (Ar‐ring), 114.36 (Ar), 118.87 (pyrrole), 119.21 (Ar‐ring), 120.64 (Ar), 127.67 (Ar), 142.13 (pyrrole), 155.7 (pyrrole), 157.82 (Ar), 162.31 (pyrrole), 170.12 (C=O). MALDI‐TOF (m/z): 966.31. Anal. calcd. for C56H46N4O12 : C, 69.56; H, 4.79; N, 5.79. Found: C, 69.98; H, 4.81; N, 5.27%. Compound 6b: Color: Metallic purple. Yield: 57%. UV/Vis (CH3OH, λmax, nm): 209, 351, 418, 518, 555, 596, 653. FT‐IR (KBr, , cm‐1): 2945, 2852, 1731, 1648, 1605, 1539, 1505, 1221, 1176. 1H NMR (300 MHz, CDCl3, δ, ppm): ‐2.79 (s, 2H, pyrrole int.), 3.46 (br, 36H, O‐CH3), 4.79 (s, 24H, CH2C=O), 7.18‐7.37 (m, 8H, Ar), 8.16 (br, 4H, Ar), 8.85 (br, 4H, pyrrole). 13C NMR (75 MHz, CDCl3, δ, ppm): 51.9 (O‐CH3), 64.89 (O‐C*H2‐ C=O), 99.3 (Ar‐ring), 114.36 (Ar), 118.87 (pyrrole), 119.21 (Ar‐ring), 120.64 (Ar), 127.67 (Ar), 142.13 (pyrrole), 155.7 (pyrrole), 157.82 (Ar), 162.31 (pyrrole), 170.12 (C=O). MALDI‐ TOF (m/z): 1481.34. Anal. calcd. for C80H78N4O24 : C, 64.95; H, 5.31; N, 3.79. Found: C, 67.34; H, 5.77; N, 3.56. 2.2.4. Synthesis of generation 1 dendrimers (8a, 8b) Separately, solutions adding ethylendiamine (0.024 g, 0.4136 mmol; 0.043 g, 0.7179 mmol) to 50 mL of a 1:1 (v:v) methanol:benzene mixture of compounds 6a and 6b (0.1 g, 0.1034 mmol; 0.1 g, 0.0598 mmol) were prepared at 80 °C with constant stirring for 36 h. 52 Ramírez et al. / European Journal of Chemistry 7 (1) (2016) 49‐55 Scheme 2 The formation of the product was corroborated by thin layer chromatography and it was purified by drying the solution in a rotary evaporator and precipitating it with a dichlorometane:hexane (1:1, v:v) solution, obtaining the generation 1 dendrimer 8a, 8b as a purple powder (Scheme 2). Compound 8a: Color: Purple. Yield: 94%. UV/Vis (CH3OH+ CH2Cl2, λmax, nm): 233, 267, 433, 556, 596, 654, 716. FT‐IR (KBr, , cm‐1): 3360, 3316, 2948, 1671, 1603, 1504, 1239, 1169, 1059. 1H NMR (300 MHz, DMSO‐d6, δ, ppm): ‐2.64 (s, 2H, pyrrole int.), 1.96 (t, 8H, NH2), 2.99 (br, 8H, CH*2‐NH2), 3.54 (br, 8H, NH‐CH2*), 4.01 (s, 8H, CH2‐C=O), 7.17‐7.21 (m, 8H, Ar), 7.37 (s, 8H, Ar), 8.04 (br, 4H, NH), 8.80 (br, 8H, pyrrole). 13C NMR (75 MHz, DMSO‐d6, δ, ppm): 38.74 (CH2‐NH2), 48.97 (NH‐ CH2), 67.41 (C*H2‐C=O), 102.44 (methine), 116.72 (Ar), 118.97 (pyrrole), 122.14 (Ar), 123.41 (Ar‐ring), 127.26 (Ar), 130.79 (Ar), 143.32 (pyrrole), 159.48 (Ar‐ring), 163.16 (pyrrole), 173.49 (C=O). MALDI‐TOF (m/z): 1080.88. Anal. calcd. for C60H62N12O8 : C, 66.77; H, 5.79; N, 15.57. Found: C, 67.02; H, 5.76; N, 15.32%. Compound 8b: Color: Purple. Yield: 34%. UV/Vis (CH3OH+ CH2Cl2, λmax, nm): 204, 317, 418, 527, 561, 599, 687. FT‐IR (KBr, , cm‐1): 3249, 2945, 2871, 1657, 1602, 1532, 1503, 1224, 1173. 1H NMR (300 MHz, DMSO‐d6, δ, ppm): ‐2.91 (s, 2H, pyrrole int.), 2.84 (br, 24H, NH2), 3.12 (s, 48H, NH‐CH*2‐CH*2‐ NH2), 4.82 (br, 24H, CH2‐C=O), 7.43 (br, 8H, Ar), 8.12‐8.21 (m, 8H, pyrrole), 8.84 (br, 12H, NH). 13C NMR (75 MHz, DMSO‐d6, δ, ppm): 38.74 (CH2‐NH2), 48.97 (NH‐CH2), 67.41 (C*H2‐C=O), 102.44 (methine), 116.72 (Ar), 118.97 (pyrrole), 122.14 (Ar), 123.41 (Ar‐ring), 127.26 (Ar), 130.79 (Ar), 143.32 (pyrrole), 159.48 (Ar‐ring), 163.16 (pyrrole), 173.49 (C=O). MALDI‐TOF (m/z): 2007.95. Anal. calcd. for C92H126N28O24: C, 55.02; H, 6.32; N, 19.53. Found: C, 54.81; H, 6.64; N, 19.67%. 2.2.5. Synthesis of the functionalized generation 1 dendrimer (10a) Generation 1 dendrimer 8a (0.1 g, 0.0926 mmol) and ethyl 2‐(2‐chloroacetamido)‐4‐thiazole acetate (0.3715 mmol) were added to 20 mL of benzene. The reaction was cooled down at room temperature with constant stirring. The coupling was instantaneous, obtaining compound 10a (Scheme 3). Color: Pink. Yield: 91%. 1H NMR (300 MHz, CDCl3+DMSO‐d6, δ, ppm): ‐2.74 (s, 2H, pyrrole int.), 1.28 (s, 12H, CH2‐CH3*), 2.58 (s, 8H, NH‐CH2), 2.86 (br, 8H CH2‐C=O), 3.68 (s, 16H, CH2‐C=O, CH2‐ NH), 4.13 (s, 8H, CH2*‐CH3), 4.86 (s, 8H, CH2‐C=O), 6.67 (s, 4H, thiazole ring), 6.82 (s, 4H, NH‐thiazole ring), 7.31 (s, 8H, Ar), 7.51 (s, 8H, Ar), 7.97 (s, 8H, pyrrole), 9.81 (br, 8H, NH). 13C NMR (75 MHz, CDCl3+DMSO‐d6, δ, ppm): 13.59 (CH2‐CH3), 36.6 (CH2C=O), 39.77 (NH‐CH2), 40.05 (CH2‐NH), 51.4 (CH2‐C=O), 60.2 (CH2‐CH3), 66 (CH2‐C=O), 112.4 (methine), 122 (CH, ring‐ CH2), 128 (Ar), 134.6 (CH=CH, ring), 143.8 (pyrrole), 145 (Ar), 151 (pyrrole) 157.03 (C‐O), 161 (N‐CH‐S, ring), 164.24 (C=O), 169.55 (C=O), 173 (C=O). MALDI‐TOF (m/z): 1997.67. Anal. calcd. for C97H104N20O20S4 : C, 58.30; H, 5.25; N, 14.02. Found: C, 58.45; H, 5.41; N, 13.71%. 3. Results and discussion 3.1. Synthesis Porphyrin‐3a and 3b were synthesized by a condensation reaction between pyrrole (1) and 2‐methoxybenzaldehyde (2a) and 2,4,6‐trimethoxybenzaldehyde (2b). The reaction was performed for 35 min at 80 °C by means of a microwave reactor Monowave 300. Compounds 3a and 3b were obtained as very intense purple powders with an approximate yield of 3%, Scheme 1. The obtained porphyrins (compounds 3a and 3b) were characterized firstly by UV‐vis spectrometry, finding five typical porphyrin bands: a high intensity band known as the Soret band appears at 420 nm and four low intensity bands, known as the Q bands, are located between 500 and 700 nm; at 200 and 230 nm, two bands can be seen, which correspond to the aliphatic chains for both compounds. The structures were confirmed by 1H and 13C NMR, where the most important signals for internal protons in the porphyrine group appeared at δ ‐2.82 ppm for compound 3a, and at δ ‐2.84 ppm for compound 3b. N NH O HN NH2 O NH NH2 O O 8a After per obtaining th continued bu 2. The dend 13C NMR, IR, that all the d MALDI‐TOF Figure 1. Compoun where the f observed. A internal pyr multiplet at the porphyri to twenty‐fo periphery o corresponds between the assigned to group. For e δ 7.43 ppm. twelve proto N HN O N H N O O NH H2N O rforming the de e unprotected uilding the mac drimer structu and MALDI‐TO dendrimers had mass spectru nd 8b was cha following repr A broad signal rrolic N‐H pr δ 8.12‐8.21 pp in ring. A broad our protons o of the dendrim to forty eigh e amine groups twenty‐four C ight aromatic p Finally, a broad ons of a seconda Ramírez et NH2 H Cl eprotection rea porphyrins, co cromolecules (d res were also c OF mass spectro d an expected m m of compoun aracterized by resentative mo at δ ‐2.75 p rotons inside pm corresponds d signal at δ 2.8 of primary am mer; the singl ht protons of s. A broad sign H2 protons lin protons, a broa d signal at δ 8.8 ary amine (NH) al. / European Jo S N O O O HN Benzene, 25 °C 9 Figure 1.MAL action using BBr mpounds 4a an dendrimers), Sc confirmed by 1 ometry. It was molecular weigh nd 8a is show 1H NMR (Figu olecule signals ppm correspon the macrocyc s to eight proto 84 ppm corresp mines (NH2) in let at δ 3.12 the CH2‐CH2 c nal at δ 4.82 p ked to the car d signal is loca 84 ppm is assign ). ournal of Chemis N S O O Scheme 3 LDI‐TOF spectrum r3 and nd 4b cheme H and found ht. The wn in ure 2), were nds to cle; a ons of ponds n the ppm chains ppm is rbonyl ated at ned to the hete Sch pro 4. In solu con thes wat neu usin pro obt per elem gen exc mat stry 7 (1) (2016) H N N H O N O O H N O S of compound 8a. In order to in dendrimer br erocyclic rings heme 3. The present w ocess of the por n order to reac utions such as ncentrations bet se negligible co ter solutions. T utral pH (6.1‐7.8 ng a nylon mem ocess, the oxid ained by the X‐ The X‐ray pho rform a surfa mental analysi nerate an emp ellent quantitat terials. 49‐55 N NH N HN O O O HN HN O O NH HN O O N H O N S N H O N S O 10a ncrease the num ranches to for s with N and S work was aime rphyrine‐dendr h this goal, diff s CoCl2, CuSO4 tween 2 and 5 p oncentrations a The removing p 8) conditions an mbrane with 0. dation states o ray photoelectr otoelectron sp ce‐sensitive‐qu is. The XPS te pirical formula tive accuracy fr O N H H NO O N S O O mber of active rm bonds with S elements we ed at studying rimer‐metal com ferent salts solu 4, NiCl2 and A ppm were used are hard to be rocess was car nd at room tem 45 µm pores fo of the formed ron spectroscop ectroscopy (XP uantitative‐spec echnique is w a because it rom homogene 53 N H N S O O centers inside h metals, new ere introduced, the formation mplex, Scheme uble in aqueous AgC2H3O2 with d. In most cases, removed from rried out under mperature. After or the filtration species were py technique. PS) allowed to ctroscopic and widely used to readily yields eous solid‐state e w , n e s h , m r r n e o d o s e 54 O N O O N S O O In our ca peaks (Figur reduce the c 368.18 and 3 An Ag‐O dou 13.12%. N N H N H N O O NH HN O NH HN O H N O O NH O N S NH O N 10a ase, through the re 3), it was co cation to its m 374.19 eV corr ublet at 367.34 a R N NH O H N N HO HN O N S O e analysis of hig rroborated tha metallic state, w responds to Ag0 and 373.27 eV w Ramírez et al. / E Figure 2. 1H H N O N S O O O O gh resolution X at NaBH4 was a where the doub 0 present at 86 was also observ uropean Journal H NMR spectrum of AgNO3 11 Scheme 4 XPS Ag able to blet at 6.88%. ved at 4. C mic spe spe l of Chemistry 7 ( f compound 8b. N O N SH O O AgNO3 NO O Conclusion New porphyr crowave meth ectrophotometr ectrometry. (1) (2016) 49‐55 N N ON N O N N O O N O N HS N O AgNO3 AgNO3 AgNO3 AgNO 3 O3NAg N NH O H NN H O NH NH O O NH O N S O O H N O N S ins were succ od, which wa y, FT‐IR, 1H N N O N N O O N N O O N O O O O O O3 N Ag AgNO3 O3 N Ag O3 O3NAg 12a NaBH4 THF, 25 °C, N2 H N HN O H N N HO O HN NH O HN O NS O O H N O 14a 13 cessfully synth as corroborate and 13C NM N H S N O N HS O O g AgNO3 AgNO3 AgNO3 N S O O hesized by the ed by UV‐vis MR and mass e s s Figure 3. The micr to achieve in reaction tim four new Porphyrin‐3 generation achieving ve each stage. F ramifications successfully. dendrimer‐m finding that (18.94%), C dendrimer‐m chemical red and with p periphery w forming bon was found i metal and it Co, which w phase. Porp capacity of fo with the de metal cation Acknowledg This wo Tecnología Instituto Pol References [1]. With, T. [2]. Smith, K York, 19 [3]. Gomes, A [4]. Kuvshin General [5]. Temelli, [6]. Dezham 2010, 1( [7]. Kingston Washing [8]. Choi, J. Y Bull. Kor [9]. Tella, A.; [10]. 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