Photoacoustic imaging of elevated glutathione in models of lung cancer for companion diagnostic applications.

Companion diagnostics (CDx) are powerful tests that can provide physicians with crucial biomarker information that can improve treatment outcomes by matching therapies to patients. Here, we report a photoacoustic imaging-based CDx (PACDx) for the selective detection of elevated glutathione (GSH) in a lung cancer model. GSH is abundant in most cells, so we adopted a physical organic chemistry approach to precisely tune the reactivity to distinguish between normal and pathological states. To evaluate the efficacy of PACDx in vivo, we designed a blind study where photoacoustic imaging was used to identify mice bearing lung xenografts. We also employed PACDx in orthotopic lung cancer and liver metastasis models to image GSH. In addition, we designed a matching prodrug, PARx, that uses the same SNAr chemistry to release a chemotherapeutic with an integrated PA readout. Studies demonstrate that PARx can inhibit tumour growth without off-target toxicity in a lung cancer xenograft model.

Spatiotemporal Control of Supramolecular Polymerization and Gelation of Metal-Organic Polyhedra.

In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA) and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption, and 1H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.

Effect of Co60 irradiation on the degradation and mineralization of sulfonated aromatic compounds in aqueous solutions.

As sulfonated aromatic compounds are widely used in industry, they have frequently been detected in aquatic environments. This study evaluated the degradation and mineralization of 2,6-naphthalenedisulfonic acid disodium salt (2,6-NS), sodium 2-naphthalenesulfonate (2-NS), benzenesulfonic acid sodium salt (BS), and 4-vinylbenzene sulfonate sodium (4-VBS) by exposing aqueous solutions of these compounds to Co60 irradiation. The radiolytic degradation of these pollutants was found to follow pseudo-first-order kinetics. The dose required to achieve 90% degradation (D90) of these four sulfonated compounds was 0.480 (2,6-NS), 0.390 (2-NS), 0.194 (BS), and 0.280 kGy (4-VBS). The chemical radiolytic yield (Gvalue) decreased as the absorbed dose increased; moreover, the chemical structures of these compounds affected their radiolytic efficacy. No significant reduction in radiolytic degradation was observed in the presence of inorganic anions (SO42-, Cl-). The radiolytic degradation efficiency was higher when hydrogen peroxide (H2O2, a hydroxyl radical (OH) promoter) was added. The results also showed that combining H2O2, persulfate anions (S2O82-, a sulfate radical anion (SO4-) promoter), or N2O gas (a OH radical promoter) with the sulfonated compounds enhanced the radiolytic mineralization yield and process by reducing the required irradiation energy. In terms of the Co60/O2 system, at an absorbed dose of 12 kGy, the total organic carbon (TOC) removal efficiency was almost 70%, resulting in the observed release of SO42- anions. In addition, the concentration of dissolved oxygen decreased and the pH was lowered. Based on these results, irradiation with Co60 was found to be a useful tool to remedy wastewater containing sulfonated aromatic compounds.

Cationic and radical intermediates in the acid photorelease from aryl sulfonates and phosphates.

The irradiation of a series of phenyl sulfonates and phosphates leads to the quantitative release of acidity with a reasonable quantum yield (≈0.2). Products characterization, ion chromatography analysis and potentiometric titration are consistent with the intervening of two different paths in this reaction, viz. cationic with phosphates and (mainly) radical with sulfonates.

Hydrolytic and photoinduced degradation of tribenuron methyl studied by HPLC-DAD-MS/MS.

The paper studies, with the help of HPLC-DAD-MS/MS technique, the hydrolytic and photoinduced degradation processes that take place in aqueous solutions of tribenuron methyl, both when preserved in the dark and when undergoing solar box irradiation under conditions that simulate sun light. The results indicate that the degradation products formed by hydrolysis alone and by photoirradiation are the same, but kinetics of the hydrolysis reaction is much slower. The degradation products are identified as 2-methoxy-4-methylamino-6-methyl-1,3,5-triazine (P1), methyl 2-aminosulfonylbenzoate (P2), and saccharin (P3) and quantified. Ecotoxicological biotests performed on 0.1 microg L(-1) photoirradiated solutions of the herbicide give a border line toxicity situation comparable to that of the precursor and indicate that the herbicide is characterized by low persistence in the environment, as required. Its degradation, however, does not lead to mineralization but to the formation of products of comparable toxicity. To evaluate the matrix effects, the photodegradation of the herbicide is also studied in the presence of rice paddy waters: the process is slower than in ultrapure water but leads to the same products. Experiments performed for comparison by irradiating ultrapure water solutions with UV lamp (254 nm) show that the degradation process is not only faster with respect to sunlight, but gives a different pathway, without in anyway leading to mineralization.

Decomposition of 2-naphthalenesulfonate in aqueous solution by ozonation with UV radiation.

This study investigates the ozonation of 2-naphthalenesulfonate (2-NS) combined with ultraviolet (UV) radiation. Naphthalenesulfonic acids are of importance as dye intermediates for the dye and textile auxiliary industries. Its derivatives, such as 2-NS, have been found in rivers and tannery effluents causing pollution problems. Thus, the 2-NS is of concern for the aquatic pollution control especially in the surface and waste waters. Ozonation combined with UV radiation is employed for the removal of 2-NS in the aqueous solution. Semibatch ozonation experiments were proceeded under different reaction conditions to study the effects of ozone dosage and UV radiation on the oxidation of 2-NS. The concentrations of 2-NS and sulfate are analyzed at specified time intervals to elucidate the decomposition of 2-NS. In addition, values of pH and oxidation reduction potential are continuously measured in the course of experiments. Total organic carbon is chosen as a mineralization index of the ozonation of 2-NS. The mineralization of 2-NS via the ozonation is remarkably enhanced by the UV radiation. These results can provide useful information for the proper removal of 2-NS in the aqueous solution by the ozonation with UV radiation.