Supplementary Methods Synthesis of pyropheophorbide-lipidIn a standard reaction, 100 nmol of 1-palmitoyl-2-hydroxy-sn-glycero-3-phosphocholine (Avanti Polar Lipids), 50 nmol pyropheophorbide (prepared from Spirulina Pacifica algae as described previously;Zheng et al., Bioconj. Chem., 2002, 13-392), 50 nmol of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (Sigma), 25 nmol of 4-(dimethylamino) pyridine (Sigma) and 50 µL of N,Ndiisopropylethylamine (Sigma) were combined in 10 mL of anhydrous dichloromethane. The reaction mixture was stirred at room temperature under argon in the dark for 48 hours. The solvent was evaporated and the residue was subjected to thin layer chromatography purification (20 x 20 cm pre-coated silica gel plate with fluorescent indicator, 1.5 mm in thickness). Chloroform-methanol-glacial acetic acid-water 65:25:8:2 (volume ratio) was used as the solvent. The major band with R f =0.4 was isolated from the plate and eluted giving a final yield of 45%. Recently, we found that improved purification could be achieved by using diol modified silica (Sorbtech) and eluting the product with 8% methanol in DCM after washing out impurities with 2% and 5% methanol in DCM. The pyropheophrobide-lipid was then dried under
Targeted delivery of intracellularly active diagnostics and therapeutics in vivo is a major challenge in cancer nanomedicine. A nanocarrier should possess long circulation time yet be small and stable enough to freely navigate through interstitial space to deliver its cargo to targeted cells. Herein, it is shown that by adding targeting ligands to nanoparticles that mimic high-density lipoprotein (HDL), tumor-targeted sub-30-nm peptide-lipid nanocarriers are created with controllable size, cargo loading, and shielding properties. The size of the nanocarrier is tunable between 10 and 30 nm, which correlates with a payload of 15-100 molecules of fluorescent dye. Ligand-directed nanocarriers targeting epidermal growth factor receptor (EGFR) are confirmed both in vitro and in vivo. The nanocarriers show favorable circulation time, tumor accumulation, and biodistribution with or without the targeting ligand. The EGFR targeting ligand is proved to be essential for the EGFR-mediated tumor cell uptake of the nanocarriers, a prerequisite of intracellular delivery. The results demonstrate that targeted HDL-mimetic nanocarriers are useful delivery vehicles that could open new avenues for the development of clinically viable targeted nanomedicine.
The morphology effect of ZrO 2 −CeO 2 on the performance of MnO x /ZrO 2 −CeO 2 catalyst for the selective catalytic reduction of NO with ammonia was investigated. The catalytic tests showed that the MnO x /ZrO 2 −CeO 2 nanorods achieved significantly higher NO conversions than the nanocubes and nanopolyhedra. The catalytic tests also showed that the MnO x /ZrO 2 −CeO 2 nanorods achieved a significantly higher rate constant with respect to NO conversion than that of the nanocubes and nanopolyhedra. On the nanorods, the apparent activation energy is 25 kJ mol −1 , which was much lower than the values of nanocubes and nanopolyhedra (42 and 43 kJ mol −1 ). The high resolution transmission electron microscopy showed that the nanorods predominately exposed {110} and {100} planes. It was demonstrated that the ZrO 2 −CeO 2 nanorods had a strong interaction with MnO x species, which resulted in great superiority for the selective catalytic reduction of NO. The excellent catalytic activity of the MnO x /ZrO 2 −CeO 2 nanorods should be attributed to the Mn 4+ species, adsorbed surface oxygen and oxygen vacancies which are associated with their exposed {110} and {100} planes.
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