Article pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
One-Pot Synthetic Approach toward Porphyrinatozinc and Heavy-Atom Involved Zr-NMOF and Its Application in Photodynamic Therapy Le-Le Zhou,‡ Qun Guan,‡ Yan-An Li, Yang Zhou, Yu-Bin Xin, and Yu-Bin Dong* College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, P. R. China S Supporting Information *
ABSTRACT: Herein, we report an iodine-attached Zn(II)-porphyrinic dicarboxylic building block (ZnDTPP-I2-2H, 1) that can be introduced into UiO-66 NMOF via one-pot synthetic approach to generate a new ZnDTPP-I2 doped UiO-66 type nano metal−organic framework (NMOF) of ZnDTPPI2⊂UiO-66 (2). Compared to its homologous iodine-free NMOF of ZnDTPP⊂UiO-66 (4), ZnDTPP-I2⊂UiO-66 (2) with heavy iodine atoms is a more effective nanosized photosensitizer for singlet oxygen generation under physiological conditions. As expected, 2 displayed a high photodynamic therapy efficacy for treatment of liver cancer cells in vitro.
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INTRODUCTION Photodynamic therapy (PDT) is based on the energy-specific light activation of photosensitizers (PS) to generate reactive species, in particular, reactive oxygen species (ROS) such as cytotoxic singlet oxygen (1O2), which are highly toxic to diseased cells.1 Among various PSs, metalloporphyrins are widely used as PS in PDT; their delivery efficiency to the diseased cells, however, is not very high due to their hydrophobic nature.2 Nano metal−organic frameworks (NMOFs),3 as an emerging class of porous materials, provide a unique platform for the effective loading of metalloporphyrinic moiety via in situ one-pot synthetic approach. In this way, the metalloporphyrinic linkage can be grafted on the MOF framework and, consequently, introduced into periodic and porous MOF nanoparticles (NPs). For example, Zhou et al.4 reported that the tetraporphyrin linker, which is comparable to the dimension of Zr6L12 assembly unit in UiO-MOF, can be directly introduced in the framework via reduced carboxyl-Zr6 connecting mode to generate the defected UiO-66 frameworks.5 However, the introduction of heavy atoms (Br or I) into a photosensitizer is known to have an influence over the rates of the intersystem crossing (ISC),6 the quantity of singlet oxygen generation and, consequently, the photodynamic therapy effect. So the incorporation of a heavy atom such as iodine into PS and, furthermore, into MOF NPs, is very significant and could meet therapeutic needs and profiles. In this way, the conventional PS can be nanosized by means of NMOF supports; consequently, highly efficient nano-PDT platform would be built up.7 © XXXX American Chemical Society
In this contribution, we report a defected UiO-66 type NPs (ZnDTPP-I2⊂UiO-66, 2) that contains iodine-attached Zn(II)porphyrinic dicarboxylic linkage (ZnDTPP-I2-2H, 1) via one-pot synthetic approach. The generated ZnDTPP-I2⊂UiO-66 (2) can be a highly effective nano PS in therapy for treatment of liver cancer cells in vitro.
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EXPERIMENTAL SECTION
Materials and Instrumentation. Pyrrole, benzaldehyde, 4-iodobenzaldehyde, methyl 4-formylbenzoate, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 1,3-diphenylisobenzofuran (DPBF), and 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) were purchased from TCI Chemical Ind. Develop Co. Zirconium(IV) chloride was purchased from Shanghai Macklin Biochemical Co., Ltd. Trifluoroacetic acid (TFA), p-phthalic acid (PTA), zinc acetate, potassium hydroxide, triethylamine, and acetic acid were purchased from Sinopharm Chemical Reagent Co., Ltd. Dulbecco’s modified eagle medium (DMEM), phosphate-buffered saline (PBS), Dulbecco’s phosphate-buffered saline (DPBS), heat-inactivated new born calf serum, and penicillin-streptomycin liquid were purchased from Invitrogen. All reactants were reagent grade and were used as purchased without further purification. The HepG2 cell lines were provided by Institute of Basic Medicine, Shandong Academy of Medical Sciences. Ultrapure water was prepared with an Aquapro system (18 MΩ). Infrared (IR) samples were prepared as KBr pellets, and spectra were obtained in the 400−4000 cm−1 range using a PerkinElmer 1600 FTIR spectrometer. 1 H NMR data were collected using an AM-300 spectrometer. Chemical shifts are reported in δ relative to tetramethylsilane (TMS). Received: December 20, 2017
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DOI: 10.1021/acs.inorgchem.7b03204 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
3129(w), 3056(w), 2943(w), 2840(w), 1726(s), 1606(m), 1553(m), 1474(w), 1432(m), 1400(m), 1347(w), 1307(w), 1266(m), 1220(w), 1211(w), 1178(m), 1112(m), 1097(m), 1062(w), 1036(m), 961(m), 843(s), 815(w), 797(m), 759(m), 730(m), 602(w), 506(w), 485(w). HRMS [M + H] calcd forC48H33I2N4O4: 983.0591, found: 983.628. Anal. Calcd for C48H34I2N4O4: C, 58.55; H, 3.48; N, 5.69, found: C, 58.81; H, 3.76; N, 5.63%. 5,15-Di(4-Methoxycarbonylphenyl)-10,20-bis(4-Iodophenyl)porphine Zinc. A mixture of 5,15-di(4-methoxycarbonylphenyl)10,20-bis(4-iodophenyl)porphine (151 mg, 0.154 mmol) and Zn(OAc)2· 2H2O (269 mg, 1.23 mmol) in MeOH/CHCl3 (10 mL/40 mL) was stirred overnight. The product was purified by column on Al2O3 (eluent, methylene chloride) to generate purple crystalline solids (Yield, 98%). 1 H NMR (300 MHz, CDCl3, ppm): 4.11 (s, 6 H), 7.92−8.46 (m, 12H), 8.81−8.85 (d, 8H). IR (KBr pellet cm−1): 3108(w), 2950(w), 2798(w), 2072(w), 1805(w), 1723(m), 1703(s), 1606(m), 1520(w), 1480(w), 1433(w), 1386(w), 1337(w), 1311(w), 1271(m), 1204(w), 1115(w), 1072(w), 1060(w), 996(s), 887(w), 850(w), 822(w), 810(w), 794(m), 763(m), 718(s), 638(w), 570(w), 490(w), 456(w). HRMS [M + H] calcd for C48H31I2N4O4Zn: 1044.9726, found: 1044.498. Anal. Calcd for C48H32I2N4O4Zn: C, 55.01; H, 3.08; N, 5.35, found: C, 55.38; H, 3.37; N, 5.18%. 5,15-Di(4-carboxyphenyl)-10,20-bis(4-Iodophenyl)porphine Zinc (ZnDTPP-I2-2H, 1). A mixture of 5,15-di(4-methoxycarbonylphenyl)-10,20-bis(4-iodophenyl)porphine zinc (151 mg, 0.144 mmol) and aqueous KOH solution (7 wt %, 15 mL) in tetrahydrofuran (THF; 35 mL) was stirred at 70 °C overnight. Then, the pH value of the system was adjusted to 1−2 by HCl (2 M) to provide purple crystalline solids (Yield, 96%). 1H NMR (300 MHz, CDCl3, ppm): 7.90−8.20 (dd, 8H), 8.20−8.40 (dd, 8H), 8.79, 8.81 (d, 8H), 13.25 (s, 2H). IR (KBr pellet cm−1): 2924(m), 1732(m), 1694(s), 1606(m), 1567(w), 1479(w), 1428(m), 1337(m), 1314(m), 1295(m), 1206(m), 1179(w), 1087(w), 998(s). 795(m), 767(w), 719(m). HRMS [M + H] calcd for C46H27I2N4O4Zn: 1016.9413, found: 1016.465. Anal. Calcd for C46H28I2N4O4Zn: C, 54.17; H, 2.77; N, 5.49, found: C, 54.30; H, 2.70; N, 5.52%. Synthesis of ZnDTPP-I2⊂UiO-66 (2). A solution of ZrCl4 (19.6 mg, 0.08 mmol), PTA (13.28 mg, 0.08 mmol), HOAc (120 μL), and
Fluorescence spectra were obtained with FLS-920 Edinburgh Fluorescence Spectrometer with a xenon lamp. The inductively coupled plasma (ICP) measurements were obtained on Thermo Scientific iCAP 7000 ICP-OES. The scanning electron microscopy (SEM) micrographs and energy-dispersive X-ray spectra (EDS) were recorded on a Gemini Zeiss Supra TM scanning electron microscope. The X-ray diffraction (XRD) experiments were obtained on a D8 ADVANCE X-ray powder diffractometer with Cu Kα radiation (λ = 1.5405 Å). Confocal fluorescence imaging studies were performed with a Leica TCS SP8 confocal laser scanning microscopy (Leica Co., Ltd. Germany) with an objective lens (×20). Mass spectrometry (MS) spectra were obtained by Bruker maxis ultrahigh resolution-time-of-flight (TOF) MS system. Elemental microanalyses (EA) were performed on Vario EL cube elemental analyzer. 2,2′-((4-Iodophenyl)methylene)bis(1H-pyrrole). A mixture of pyrrole (0.43 mol, 30 mL), 4-iodobenzaldehyde (2.737 g, 11.8 mmol), and TFA (90 μL) was stirred in dark under N2 atmosphere for 15 min. The product was purified by column on silica gel (methylene chloride/ petroleum ether = 1:1 (v/v) to provide the product as white crystalline solids (Yield, 60%). 1H NMR (300 MHz, CDCl3, ppm): 5.44 (s, 1H), 5.91 (s, 2H), 6.18 (d, 2H), 6.73 (s, 2H), 6.9−7.7 (dd, 4H), 7.94 (s, 2H). IR (KBr pellet cm−1): 3328(s), 3128(w), 3097(w), 2857(w), 1553(w), 1486(m), 1456(w), 1399(m), 1311(w), 1282(w), 1259(w), 1188(w), 1114(w), 1096(w), 1063(w), 1025(m), 1007(m), 885(w), 837(w), 780(m), 761(m), 731(m), 602(w), 581(w), 507(w). High-resolution (HR) MS [M + H] calcd for C15H14IN2: 349.0202, found: 349.0179. Anal. Calcd for C15H13IN2: C, 51.74; H, 3.76; N, 8.05, found: C, 51.93; H, 3.32; N, 7.98%. 5,15-Di(4-Methoxycarbonylphenyl)-10,20-bis(4-Iodophenyl)porphine. A mixture of methyl 4-formylbenzoate (0.22g, 1.35 mmol), 2,2′-((4-iodophenyl)methylene)bis(1H-pyrrole) (0.3 g, 0.86 mmol), and TFA (200 μL) in methylene chloride (120 mL) was stirred overnight. After addition of DDQ (0.31 g, 1.35 mmol), the mixture was stirred for additional 1 h. Then, the reaction was quenched by NEt3 (4 mL). The product was purified by column on Al2O3 (eluent, methylene chloride) to generate purple crystalline solids (Yield, 14%). 1H NMR (300 MHz, CDCl3, ppm): 2.87 (s, 2H), 4.12 (s, 6H), 7.92−8.46 (m, 12H), 8.81−8.85 (d, 8H). IR (KBr pellet cm−1): 3322(s),
Scheme 1. Synthesis of 1
B
DOI: 10.1021/acs.inorgchem.7b03204 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
absorbance at 414 nm due to the 1O2 produced by the porphyrininduced porphyrin. To characterize the difference in the rate of 1O2 produced by different samples, the ratio A/A0 of absorbance A and the initial absorbance A0 at 414 nm at different irradiation times was calculated and plotted as the ordinate for the irradiation time t. The same concentrations of DMF dispersions or solutions of 1−4 without DPBF were used as the references for UV−vis measurement. Cell Imaging. The HepG2 cells were grown in DMEM (Invitrogen) containing 10% heat-inactivated new born calf serum, 100 U/mL penicillin, and 100 μg/mL streptomycin in an atmosphere of 5% CO2 and 95% air at 37 °C. For confocal fluorescence imaging, cells were incubated in glass-bottom dishes for 24 h. Cells were incubated at 37 °C with 2 (10 μg/mL) in PBS for 1 h in an atmosphere of 5% CO2 and 95% air, then washed with PBS, and fluorescence images were captured. Samples were excited with two lasers (405 nm for metal− organic framework (MOF) and 514 nm for ZnDTPP-I2) and collected with two groups of channels (450−500 nm for green channel and 630−680 nm for red channel), respectively. Phototoxicity. A suitable number of HepG2 cells were transferred to a 96-well plate with a cell number of ∼5000 cells/well and incubated overnight. After removal of the culture medium, the cells were incubated with MOF dispersion (200 μL, concentration gradient 0−80 μg/mL) for 1 h. The dispersion was removed, DPBS (200 μL) was added to each well, and the green LED lamp (20 mW/cm2) was irradiated for 10 min. After removal of DPBS, DMEM high-glucose medium (200 μL) was added to each well. After incubation for 24 h, MTT (10 μL, 5 mg/mL) was added and left for 4 h. The supernatant was removed by centrifugation. The precipitate was dissolved in dimethyl sulfoxide (DMSO; 150 μL), and the absorbance at 490 nm was measured. Dark Toxicity. A suitable number of HepG2 cells was transferred to a 96-well plate with a cell number of ∼5000 cells/well and incubated overnight. After removal of the culture medium, the cells were incubated with MOF dispersion (200 μL, concentration gradient 0−80 μg/mL) for 1 h. The dispersion was removed, and every well was washed once with DPBS (200 μL). After removal of DPBS, DMEM high-glucose medium (200 μL) was added to each well. After incubation for 24 h, MTT (10 μL, 5 mg/mL) was added and left for 4 h. The supernatant was removed by centrifugation. The precipitate was dissolved in DMSO (150 μL), and the absorbance at 490 nm was measured.
ZnDTPP-I2-2H (1, 40 mg) in dimethylformamide (DMF; 3.2 mL) was heated at 120 °C under static conditions. After 24 h, the reaction system was cooled to room temperature, and the precipitate was isolated by centrifugation. The solid was washed by fresh DMF until colorless and washed with acetone for additional three times. Finally, the solids were dried in air. IR (KBr pellet cm−1): 3392 (s), 2929 (m), 1661 (s), 1586 (s), 1505 (m), 1397 (s), 1254 (w), 1156 (w), 1098 (w), 1061 (w), 1017 (w), 965 (w), 800 (w), 747 (m), 662 (m), 548 (w), 482 (w). Elemental analysis data (%): C, 43.55; H, 1.89; N, 0.09. ICP analysis indicated that the Zn content was 0.09 wt %, corresponding to doped 1.4 wt % of I-substituted Zn(II)-porphyrin. Singlet Oxygen Generation Measurement. In vitro single oxygen generation measurement was performed by modified method using DPBF as capture agent. An amount of 2 mL of DMF containing 100 μL of DPBF (1 mM) and corresponding photosensitizer samples (1−4) was used in a quartz cuvette. Drums O2 for 1 min under a green light-emitting diode (LED; ca. 540 nm, 20 mW/cm2) at room temperature for 2 min. The absorbance intensity of DPBF at 414 nm in the mixture was recorded at 15 s intervals. The rate of singlet oxygen generation was determined from the reduced absorbance intensity over time. For the control experiments, DPBF absorption was also recorded for negative comparison at the same conditions in the absence of photosensitizer. DPBF was observed to have a significant decrease in
Scheme 2. Synthesis of 2
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RESULTS AND DISCUSSION We hypothesized that the metalloporphyrinic moiety doped UiO-66 NMOF ZnDTPP-I2⊂UiO-66 (2) could be the ideal PS Scheme 3. Control Experiments for Demonstrating the Location of ZnDTPP-I2 Linkage in 2a
a
The obtained samples were thoroughly washed with DMF and acetone to remove remaining porphyrinic species and dried in air. PXRD patterns of the samples are identical to that of UiO-66 and 2, indicating the structural integrity and crystallinity of UiO-66 were maintained during the experimental processes. C
DOI: 10.1021/acs.inorgchem.7b03204 Inorg. Chem. XXXX, XXX, XXX−XXX
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(0.08 mmol), ZnDTPP-I2-2H (1, 0.04 mmol), and HOAc (120 μL) in DMF (3.2 mL) under solvothermal conditions. The generated crystalline solids remained deep brown after completely washing with DMF and acetone (Scheme 2), indicating that the ZnDTPP-I2 species existed in the defected MOF matrix of 2 and that some positions where the Zr6(PTA)12 moiety belonged were occupied by the less coordinated but sizable ZnDTPP-I2 linkages in the framework.4 The involved ZnDTPP-I2 amount is 1.4 wt % (Zn, 0.09 wt %) based on the ICP measurement. For further demonstrating the location of ZnDTPP-I2 in MOF, control experiments were designed and performed. As shown in Scheme 3, ZnDTPP-I2 content in the sample obtained by impregnating method based on ZnDTPP-I2-2H was only 0.06 wt %, indicating that the trace amount of ZnDTPP-I2 resulted from a postsynthetic surface decoration.4 Meanwhile, no ZnDTPP-I2 species was detected in the sample based on ZnDTPP-I2-2Me, which was generated by the solvothermal method used for synthesis of 2. On the one hand, the result indicated that −CO2H was essential for the porphyrinic species
candidate for singlet oxygen generation and PDT in living cells. First, the PS of ZnDTPP-I2 is highly dispersed in the UiO-66 matrix and could effectively avoid the aggregation-caused quenching (ACQ);8 second, the heavy atom introduction of iodine would reasonably promote the ISC rate and, consequently, enhance the singlet generation efficiency; third, the porous UiOframework could facilitate the generated singlet oxygen release; fourth, UiO-MOFs have low toxicity,9 and they can be easily scaled down to nanoregimes ( 0.05). On the other hand, ZnDTPP-I2⊂UiO-66 (2) exhibited a dramatic decline in cell viability after irradiation. Figure 5 showed that the cell viability decreased to less than 50% for HepG2 when the
cells (HepG2) were selected and visualized by using a green channel for NMOF (λex = 405 nm) and a red channel for F
DOI: 10.1021/acs.inorgchem.7b03204 Inorg. Chem. XXXX, XXX, XXX−XXX
Inorganic Chemistry concentration of 2 was at 10 μg/mL (equivalent to 0.14 μg/mL of ZnDTPP-I2). Notably, with the increase of concentration of 2 to 40 μg/mL (equivalent to 0.56 μg/mL of ZnDTPP-I2), the cell viability decreased to less than 25% for the HepG2 cells after irradiation. Recently, some very impressive works of porphyrinic NMOFbased PSs for photodynamic therapy have been reported, which are summrized in Table 1. Compared to the reported porphyrinic
DBP-UiO DBC-UiO Hf-PCN-224 PS@MOF Zr-PCN-224
light source (mW/cm2)
cell lines
time (min)
PS (μM)
MTT (%)
LED, 640 nm (100) LED, 640 nm (100) laser, 661 nm (5) laser, 660 nm (100) laser, 420 nm; 630 nm (100) laser, 420 nm (100)
SQ20B CT26 4T1 HeLa HeLa
15 15 30 15 30
20 15 101 3.5 1.75
25 25 20 30 25
13 14 15 16 17
B16
30
30
30
18
CT26 HepG2
15 10
10 38
25 25
19 20
HepG2
10
25
this work
TCPP/ BCDTEUiO-66 TBC-Hf LED, 650 nm (100) DOX@ laser, 655 nm (300) NPMOF ZnDTPPgreen LED, I2⊂UiO-66 540 nm (20)
0.55
ref
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CONCLUSIONS In summary, we deisgned and synthesized a Zn(II)-porphyrinic dicarboxylic species (ZnDTPP-I2) doped UiO-66-type NMOF ZnDTPP-I2⊂UiO-66 via one-pot synthetic approach. In this way, the conventional PS of metalloporphyrin with heavy iodine atoms can be successfully nanosized by means of NMOF supports; consequently, highly efficient nano PDT platform would be built. The generated NMOF herein can be a highly effective nanophotosensitizer for photodynamic therapy of liver cancer cells. ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.7b03204. Photostability of 1−4, additional characterization for 2, synthesis and characterization of 3−4 (PDF)
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ACKNOWLEDGMENTS
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REFERENCES
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NMOF-based PSs, the PDT treament of 2 in living cells met low energy and convenient light source (green LED, 20 mW/cm2), tiny PS amount (0.55 μM), and short irradiation time (10 min) for less than 25% cell viability. So 2 herein is in a strong position among the porphyrinic NMOF-based PDT materials.
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We are grateful for financial support from NSFC (Grant Nos. 21671122, 21475078, and 21401118) and the Taishan Scholar’s Construction Project.
Table 1. Summary of Recent Typical Porphyrinic NMOFBased Photodynamic Therapy in Living Cells sample
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Qun Guan: 0000-0002-5522-5106 Yu-Bin Dong: 0000-0002-9698-8863 Author Contributions ‡
These authors contributed equally.
Notes
The authors declare no competing financial interest. G
DOI: 10.1021/acs.inorgchem.7b03204 Inorg. Chem. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.inorgchem.7b03204 Inorg. Chem. XXXX, XXX, XXX−XXX
