Chemotherapy agents are notorious for producing severe side-effects. One approach to mitigating this off-target damage is to deliver the chemotherapy directly to a tumor via transarterial infusion, or similar procedures, and then sequestering any chemotherapeutic in the veins draining the target organ before it enters the systemic circulation. Materials capable of such drug capture are yet to be fully realized. Here, we report the covalent attachment of genomic DNA to iron-oxide nanoparticles. With these magnetic materials, we captured three common chemotherapy agents—doxorubicin, cisplatin, and epirubicin—from biological solutions. We achieved 98% capture of doxorubicin from human serum in 10 min. We further demonstrate that DNA-coated particles can rescue cultured cardiac myoblasts from lethal levels of doxorubicin. Finally, the in vivo efficacy of these materials was demonstrated in a porcine model. The efficacy of these materials demonstrates the viability of genomic DNA-coated materials as substrates for drug capture applications.

ExperimentalMaterials. 2 M AlMe 3 in toluene (Aldrich), GaCl 3 (Aldrich), HSO 3 Cl (Aldrich), 21 nm nanopowder TiO 2 (Aldrich), 30% H 2 O 2 (EMD) were obtained commercially and used as received. The starting material 5,10, corrole (H 3 tpfc) was prepared based on the literature method.1 The solvents pyridine and toluene were dried over a column. Acetone and dichloromethane used were both of reagent and spectroscopic grades depending on the applications.Chemical Preparation. All preparations were carried out under Ar(g) atmosphere unless otherwise noted. ,17-bischlorosulfonato-5,10,15-tris(pentafluorophenyl) corrole (H 3 tpfc(SO 2 Cl) 2 ; 1) was performed according to the literature procedure. 2 The metallocorroles described in this study were prepared in the following manner. Corrole Preparation. Preparation of 2 Preparation of 1-Al.To the 20-mL toluene solution of 0.32 g of 1 (0.32 mmol) in a round bottom flask was added 0.8 mL of 2 M AlMe 3 (1.6 mmol) in toluene solution at an icebath temperature. The solution was stirred for 10 min followed by the addition of 1 mL anhydrous pyridine. The solution was allowed to stir for another 10 min over ice. The reaction was quenched by an addition of ice chips. The dark green solution was then extracted with CH 2 Cl 2 and washed with water. The solvent was removed in vacuo and the dry deep green solid was redissolved in CH 2 Cl 2 followed by filtration. The filtrate was brought to dryness to afford the dark green solid (0. Preparation of 1-Ga.To a heavy-walled Schlenk flask were added 0.20 g of 1 (0.20 mmol) and 0.57 g GaCl 3 (3.3 mmol) under Ar(g). The flask was chilled in N 2 (l) and evacuated. 15 mL Degassed anhydrous pyridine (15mL) was added to the flask via vacuum transfer. The

Globally scalable sunlight-driven devices that convert solar energy into storable fuels will require efficient light absorbers that are made of non-precious elements. Suitable photoanode materials are yet to be discovered. Here we utilised the timesaving nature of pulsed-laser in liquids synthesis and prepared a series of neat and mixed-metal tungsten oxide photoanode materials to investigate the effect of ad-metals on optical and photocurrent generation properties. We obtained sub-µm-sized materials with different colours from W, Al, Ta, or first-row transition metal targets in water or aqueous ammonium metatungstate solutions. We observed metastable polymorphs of WO3 and tungsten oxides with varying degrees of oxygen deficiency. Pulsed-laser in liquids synthesis of Ni in ammonium metatungstate solutions produced hollow spheres (with ≤ 6% Ni with respect to W). Photocurrent generation in strong aqueous acid was highest in mixed-metal tungsten oxide photoanode materials with around 5% of iron or nickel.

In an effort to develop effective new optical contrast agents, we report the synthesis of porphyrazines (pzs) of the form H(2)[pz(A(4-n);C(n))], n = 1, and 2 (trans-), where "A" represents peripheral heteroatom (S- and O-) R-groups and "C" is a fused, beta,beta'-diisopropyloxynaphtho group. The sulfide appended trans-H(2)[pz(A(2);C(2))] pz (7) has the longest wavelength absorption, approximately 874 nm (log epsilon = 4.53), and S(1) fluorescence at approximately 927 nm, wavelengths within the window of maximum tissue penetration. Emission from the oxygen-atom appended naphtho-pzs (8, 9) has been observed within carcinoma cells, confirming cellular uptake and their potential use as optical agents.

We are investigating the biological and biomedical imaging roles and impacts of fluorescent metallocorrole-TiO 2 nanoconjugates as potential near-infrared optical contrast agents in vitro in cancer and normal cell lines. The TiO 2 nanoconjugate labeled with the small molecule 2,17-bis(chlorosulfonyl)-5,10,15-tris(pentafluorophenyl)corrolato aluminum(III) (1-Al-TiO 2 ) was prepared. The nanoparticle 1-Al-TiO 2 was characterized by transmission electron microscopy (TEM) and integrating-sphere electronic absorption spectroscopy. TEM images of three different samples of TiO 2 nanoparticles (bare, H 2 O 2 etched, and 1-Al functionalized) showed similarity in shapes and sizes with an average diameter of 29 nm for 1-Al-TiO 2 . Loading of 1-Al on the TiO 2 surfaces was determined to be ca. 20-40 mg 1-Al/g TiO 2 . Confocal fluorescence microscopy (CFM) studies of luciferase-transfected primary human glioblastoma U87-Luc cells treated with the nanoconjugate 1-Al-TiO 2 as the contrast agent in various concentrations were performed. The CFM images revealed that 1-Al-TiO 2 was found inside the cancer cells even at low doses (0.02-2 µg/mL) and localized in the cytosol. Bioluminescence studies of the U87-Luc cells exposed to Corresponding authors: Karn Sorasaenee, ksorasaenee@chla.usc.edu and Harry B. Gray, hbgray@caltech.edu.Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. HHS Public Access Author Manuscript Author ManuscriptAuthor ManuscriptAuthor Manuscript various amounts of 1-Al-TiO 2 showed minimal cytotoxic effects even at higher doses (2-2000 µg/mL) after 24 h. A similar observation was made using primary mouse hepatocytes (PMH) treated with 1-Al-TiO 2 at low doses (0.0003-3 µg/mL). Longer incubation times (after 48 and 72 h for U87-Luc) and higher doses (> 20 µg/mL 1-Al-TiO 2 for U87-Luc and > 3 µg/mL 1-Al-TiO 2 for PMH) showed decreased cell viability. Graphical AbstractSynopsis for the graphic abstract Fluorescence (shown in red) from the corrole nanoconjugate 1-Al-TiO 2 internalized in the glioblastoma U87-Luc cell.