Photoactive ZnO Materials for Solar Light-Induced CuxO-ZnO Catalyst Preparation.

In this work, the solar light-induced redox photoactivity of ZnO semiconductor material was used to prepare CuxO-ZnO composite catalysts at room temperature with a control of the chemical state of the copper oxide phase. Cu2(I)O-ZnO and Cu(II)O-ZnO composite catalysts were prepared by using Cu(acac)2 in tetrahydrofuran-water and Cu(NO3)2 in water as metallic precursor, respectively. Prior to the implementation of the photon-assisted synthesis method, the most efficient photoactive ZnO material was selected from among different ZnO materials prepared by the low temperature polyol and precipitation methods with carbonates and carbamates as precipitation agents. The photocatalytic degradation of the 4-chlorophenol compound in water under simulated solar light was taken as a model reaction. The ZnO support materials were characterized by X-ray diffraction (XRD), surface area and porosimetry measurements, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the synthesis method strongly influenced their photoactivity in terms of 4-chlorophenol degradation and of total organic carbon removal. The most photoactive ZnO material was prepared by precipitation with carbonates and calcined at 300 °C, benefitting from a high specific surface area and a small mean crystallite size for achieving a complete 4-chlorophenol mineralization within 70 min of reaction, with minimum Zn2+ released to the solution. Besides thermal catalysis applications, this work has opened a new route for the facile synthesis of Cu2O-ZnO heterojunction photocatalysts that could take place under solar light of the heterojunction built between the p-type semi-conductor Cu2O with direct visible light band gap and the ZnO semiconductor phase.

Bladder cancer detection using a peptide substrate of the 20S proteasome.

The 20S catalytic core of the human 26S proteasome can be secreted from cells, and high levels of extracellular 20S proteasome have been linked to many types of cancers and autoimmune diseases. Several diagnostic approaches have been developed that detect 20S proteasome activity in plasma, but these suffer from problems with efficiency and sensitivity. In this report, we describe the optimization and synthesis of an internally quenched fluorescent substrate of the 20S proteasome, and investigate its use as a potential diagnostic test in bladder cancer. This peptide, 2-aminobenzoic acid (ABZ)-Val-Val-Ser-Tyr-Ala-Met-Gly-Tyr(3-NO2 )-NH2 , is cleaved by the chymotrypsin 20S proteasome subunit and displays an excellent specificity constant value (9.7 × 10(5)  m(-1) ·s(-1) ) and a high kcat (8 s(-1) ). Using this peptide, we identified chymotrypsin-like proteasome activity in the majority of urine samples obtained from patients with bladder cancer, whereas the proteasome activity in urine samples from healthy volunteers was below the detection limit (0.5 pm). These findings were confirmed by an inhibitory study and immunochemistry methods.

Novel internally quenched substrate of the trypsin-like subunit of 20S eukaryotic proteasome.

This article describes the synthesis, using combinatorial chemistry, of internally quenched substrates of the trypsin-like subunit of human 20S proteasome. Such substrates were optimized in both the nonprime and prime regions of the peptide chain. Two were selected as the most susceptible for proteasomal proteolysis with excellent kinetic parameters: (i) ABZ-Val-Val-Ser-Arg-Ser-Leu-Gly-Tyr(3-NO2)-NH2 (kcat/KM = 934,000 M(-1) s(-1)) and (ii) ABZ-Val-Val-Ser-GNF-Ala-Met-Gly-Tyr(3-NO2)-NH2 (kcat/KM = 1,980,000 M(-1) s(-1)). Both compounds were efficiently hydrolyzed by the 20S proteasome at picomolar concentrations, demonstrating significant selectivity over other proteasome entities.