Photocatalytic toluene oxidation with nickel-mediated cascaded active units over Ni/Bi2WO6 monolayers.

Adsorption and activation of C-H bonds by photocatalysts are crucial for the efficient conversion of C-H bonds to produce high-value chemicals. Nevertheless, the delivery of surface-active oxygen species for C-H bond oxygenation inevitably needs to overcome obstacles due to the separated active centers, which suppresses the catalytic efficiency. Herein, Ni dopants are introduced into a monolayer Bi2WO6 to create cascaded active units consisting of unsaturated W atoms and Bi/O frustrated Lewis pairs. Experimental characterizations and density functional theory calculations reveal that these special sites can establish an efficient and controllable C-H bond oxidation process. The activated oxygen species on unsaturated W are readily transferred to the Bi/O sites for C-H bond oxygenation. The catalyst with a Ni mass fraction of 1.8% exhibits excellent toluene conversion rates and high selectivity towards benzaldehyde. This study presents a fascinating strategy for toluene oxidation through the design of efficient cascaded active units.

Role of Transient Anions in Chemoradiation Therapy: Base Modifications, Cross-Links, and Cluster Damages Induced to Cisplatin-DNA Complexes by 1-20 eV Electrons.

The molecular mechanism of platinum-based drugs in concomitant chemoradiation therapy relies on enhancement of DNA damage in cancer cells, particularly that of detrimental clustered lesions and cross-links induced by the abundant low-energy electrons (LEEs) generated by ionizing radiation. We provide the complete 1-20 eV electron-energy dependence of the yields of all conformational LEE-induced lesions to biological DNA, when it binds to five molecules of the chemotherapeutic drug cisplatin. Recording at 1 eV intervals clearly show that the enhancement of all lesions is particularly intense at the energies of core-excited transient molecular anions (i.e., TMAs at 5, 6, and 10 eV). New TMAs are observed at 14 and 18 eV, only in yield functions of cisplatin-DNA complexes. Enhancements of all lesions by cisplatin are quantified over the 1-20 eV range, where maxima appear at 14 and 18 eV. The most detrimental lesions to cell survival exhibit the highest enhancements by factors of 2-3. Whereas no cluster lesions are induced by electrons of energy <5 eV in DNA, LEEs of any energy cause clustered damages in the complex. These results confirm the current notion that LEEs and TMAs play a dominant role in the molecular mechanism of platinum-drug chemoradiation therapy.

Molecular efficacy of radio- and chemotherapy sequences from direct DNA damage measurements.

PURPOSE: To investigate the molecular aspects of the synergy between ionizing radiation and platinum (Pt) chemotherapeutic agents in cancer treatment with chemoradiation therapy (CRT) by measuring damages induced by low-energy electrons (LEE) to DNA bound to cisplatin. LEE are produced abundantly by any type of ionizing radiation and cisplatin represents a typical Pt-chemotherapeutic agents. MATERIALS AND METHODS: Our strategy involves two parallel administrations of cisplatin and irradiation with a 4.6 and 9.6 eV electron fluence of 1.1 × 1012: (1) LEE bombardment of supercoiled DNA and its subsequent reaction with cisplatin; (2) the reaction of DNA with cisplatin followed by LEE irradiation. The damage yields for the loss of supercoiled (LS), single-strand breaks (SSB) and double-strand breaks (DSB) were obtained from gel electrophoresis analysis. Base modifications were revealed by treating the samples with Escherichia coli base excision repair endonuclease (Nth and Fpg). RESULTS: The yields were deduced from the respective time-response for the reaction of DNA with cisplatin. The results show that binding cisplatin to DNA followed by LEE irradiation, consistently yields more DNA damages than the reverse order. In comparison to non-treated DNA, administration (2) results in an increase of LS and SSB of 1.4-3.3 folds and of DSB by more than an order of magnitude. Furthermore, after enzyme treatment, the yields of DSB rise by factors of 5.3-15.4, indicating a large increase of clustered damages, which should at least partially translate into an increase of lethal damages in cancer cells during the CRT. CONCLUSIONS: Our results demonstrate that a strong synergy between radiation and cisplatin can only be achieved at the molecular level, if the drug is present at the time of irradiation. Furthermore, this work confirms the LEE mechanism previously proposed to explain the synergy between radiation and Pt drugs in CRT. It involves chemical sensitization of DNA prior to irradiation, to facilitate strand breaks and clustered damages induced by the highly reactive LEE.

Cleavage enhancement of specific chemical bonds in DNA by cisplatin radiosensitization.

X-ray photoelectron spectroscopy (XPS) is harnessed as an in situ efficient characterization technique for monitoring chemical bond transformation in DNA and cisplatin-DNA complexes under synergic X-ray irradiation. By analyzing the variation of relative peak area of core elements of DNA as a function of irradiation time, we find that the most vulnerable scission sites in DNA are those containing phosphate and glycosidic bonds. Compared to DNA, the effective rate constants of the corresponding phosphodiester and glycosidic bond cleavages for cisplatin-DNA complexes are 1.8 and 1.9 folds larger. These damages and their enhancements are similar to those induced by low energy electrons (LEE). Consistently, the magnitude of the secondary electron distribution produced by the X-rays on the cisplatin-DNA complexes is considerably increased compared to that of pristine DNA. The data suggest that DNA radiosensization by cisplatin results not only from the sensitization of DNA to the action of LEE, but also from an increase the production of LEE at the site of binding of the cisplatin. The results provide new insights into the mechanisms of cisplatin-induced sensitization of DNA under X-ray irradiation, which could be helpful in the design of new cisplatin-based antitumor drugs.

TiO2-graphene nanocomposites for gas-phase photocatalytic degradation of volatile aromatic pollutant: is TiO2-graphene truly different from other TiO2-carbon composite materials?

The nanocomposites of TiO(2)-graphene (TiO(2)-GR) have been prepared via a facile hydrothermal reaction of graphene oxide and TiO(2) in an ethanol-water solvent. We show that such a TiO(2)-GR nanocomposite exhibits much higher photocatalytic activity and stability than bare TiO(2) toward the gas-phase degradation of benzene, a volatile aromatic pollutant in air. By investigating the effect of different addition ratios of graphene on the photocatalytic activity of TiO(2)-GR systematically, we find that the higher weight ratio in TiO(2)-GR will decrease the photocatalytic activity. Analogous phenomenon is also observed for the liquid-phase degradation of dyes over TiO(2)-GR. In addition, the key features for TiO(2)-GR including enhancement of adsorptivity of pollutants, light absorption intensity, electron-hole pairs lifetime, and extended light absorption range have also been found in the composite of TiO(2) and carbon nanotubes (TiO(2)-CNT). These strongly manifest that TiO(2)-GR is in essence the same as other TiO(2)-carbon (carbon nanotubes, fullerenes, and activated carbon) composite materials on enhancement of photocatalytic activity of TiO(2), although graphene by itself has unique structural and electronic properties. Notably, this key fundamental question remains completely unaddressed in a recent report ( ACS Nano 2010 , 4 , 380 ) regarding liquid-phase degradation of dyes over the TiO(2)-GR photocatalyst. Thus, we propose that TiO(2)-GR cannot provide truly new insights into the fabrication of TiO(2)-carbon composite as high-performance photocatalysts. It is hoped that our work could avert the misleading message to the readership, hence offering a valuable source of reference on fabricating TiO(2)-carbon composites for their application as a photocatalyst in the environment cleanup.

Microwave hydrothermal synthesis of calcium antimony oxide hydroxide with high photocatalytic activity toward benzene.

A nanocrystalline CaSb2O5(OH)2 photocatalyst synthesized from CaCl2 and K2H2Sb2O7 was used to degrade benzene in the gas phase for the first time. The obtained sample was characterized by X-ray diffraction, N2 sorption-desorption, UV-vis diffuse reflectance spectroscopy, transmission electron microscopy, electron spin resonance, and X-ray photoelectron spectroscopy. The CaSb2O5(OH)2 sample had an average particle size of approximately 8 nm, a specific surface area of 101.8 m2 g(-1), and a band gap of 4.6 eV. Photocatalytic activity of the sample was mainly evaluated by the degradation of benzene in an O2 gas stream under ultraviolet light irradiation. The results demonstrated that the photoactivity of CaSb2O5(OH)2 was higher than that of commercial TiO2 (P25, Degussa Co.). In the photocatalytic degradation of benzene, it finally reached a steady conversion ratio of 29%. CaSb2O5(OH)2 has also exhibited activity toward other aromatic organic compounds. A possible mechanism of photocatalysis over CaSb2O5(OH)2 nanocrystals was proposed.

Photocatalytic decomposition of benzene by porous nanocrystalline ZnGa2O4 with a high surface area.

Porous nanocrystalline ZnGa2O4 catalysts were synthesized by a simple soft-chemical method at low temperature. The catalysts were characterized by XRD, nitrogen adsorption, SEM, TEM, UV/ vis, and FT-IR spectroscopy. The activity of the photocatalysts was evaluated by decomposition of benzene and its derivatives in the gas phase. It was found that hydrothermal treatment resulted in the formation of spinel ZnGa2O4 with a large surface area of 43-201 m2 x g(-1) depending on the synthetic temperature. The optimum synthetic temperature was found to be 80 degrees C, at which the sample possessed a surface area of 201 m2 x g(-1) and had the highest photocatalytic activity for degrading benzene. A comparison with TiO2 and Pt/TiO2 showed that the ZnGa2O4 (synthesized at 80 degrees C) had improved photocatalytic activity and durability over the TiO2-based catalysts. No remarkable deactivation of the ZnGa2O4 catalyst was observed in 80 h photoreaction, whereas the TiO2 deactivated remarkably in 24 h reaction. The high photocatalytic performance of porous ZnGa2O4 catalysts can be explained by the large specific surface area, the accessible porous framework, and the high redox power.

Fe-g-C3N4-catalyzed oxidation of benzene to phenol using hydrogen peroxide and visible light.

A bioinspired iron-based catalyst with semiconductor photocatalytic functions in combination with a high surface area holds promise for synthetic chemistry via combining photocatalysis with organosynthesis. Here exemplified for phenol synthesis, Fe-g-C(3)N(4)/SBA-15 is able to oxidize benzene to phenol with H(2)O(2) even without the aid of strong acids or alkaline promoters. By taking advantage of both catalysis and photocatalysis functions of g-C(3)N(4) nanoparticles, the yield of the phenol can be markedly promoted.

Nanostructuring cadmium germanate catalysts for photocatalytic oxidation of benzene at ambient conditions.

A nanostructured Cd(2)Ge(2)O(6) photocatalyst was successfully prepared by a hydrothermal process. The photocatalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV/vis, N(2) adsorption-desorption, and Fourier transform infrared (FTIR) techniques. The photocatalytic property of the material was evaluated via the decomposition of benzene in the gas phase with light illumination and was compared with that of commercial titania (Degussa P25) and Pt/TiO(2). The electronic band structure of Cd(2)Ge(2)O(6) was analyzed by density functional theory (DFT) calculation. Results reveal that the prepared Cd(2)Ge(2)O(6) has unique geometric and electronic properties, which in combination with its superior textural properties makes it a new semiconductor photocatalyst for environmental purification of benzene in air with molecular oxygen under ambient conditions. It was also found that the Cd(2)Ge(2)O(6) was more active and stable than TiO(2)-based catalysts in the photocatalytic decomposition of other volatile aromatic pollutants including toluene and ethylbenzene. The enhanced photocatalytic performance of Cd(2)Ge(2)O(6) can be explained by the special band structure, and geometric and electronic feature, in unison with the high surface area nanoporous framework.

Efficient degradation of benzene over LaVO4/TiO2 nanocrystalline heterojunction photocatalyst under visible light irradiation.

A nanocrystal heterojunction LaVO4TiO2 visible light photocatalyst has been successfully prepared by a simple coupled method. The catalyst was characterized by powder X-ray diffraction, nitrogen adsorption-desorption, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectra, photoluminescence, and electrochemistry technology.The results showed that the prepared nanocomposite catalysts exhibited strong photocatalytic activity for decomposition of benzene under visible light irradiation with high photochemical stability. The enhanced photocatalytic performance of LaVO4/TiO2 may be attributed to not only the matched band potentials but also interconnected heterojunction of LaVO4 and TiO2 nanoparticles.

Degradation of benzene over a zinc germanate photocatalyst under ambient conditions.

A rod-shaped Zn2GeO4 photocatalyst has been successfully prepared by a surfactant-assisted hydrothermal method. The photocatalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, UV/vis, N2 adsorption-desorption, and FTIR techniques. The photocatalytic activity of the sample was evaluated by the decomposition of benzene in the gas phase under UV light illumination and was compared with that of bulk Zn2GeO4, commercial titania (Degussa P25), and Pt/P25. The results revealed that the Zn2GeO4 nanorods had the best photocatalytic activity for mineralizing benzene to CO2 among the catalysts examined. No obvious deactivation of Zn2GeO4 nanorods was observed during the prolonged operation of 140 h. It was found that the Zn2GeO4 was also more active and stable than TiO2-based catalysts toward photocatalytic decomposition of other volatile aromatic pollutants (e.g., toluene and ethylbenzene).

A mononuclear cyclopentadiene-iron complex grafted in the supercages of HY zeolite: synthesis, structure, and reactivity.

The reaction of ferrocene with the acidic hydroxy groups in the supercages of zeolite HY dehydrated at 673 K and the reactivity of the resultant surface species towards CO and O(2) were investigated by temperature-programmed decomposition (TPD) and reduction (TPR) and IR, X-ray absorption fine structure analysis (XAFS), and X-ray photoelectron (XP) spectroscopy. In situ FTIR, TPD, TPR, and chemical analysis reveal that the Cp(2)Fe molecule adsorbed on the zeolite surface loses one cyclopentadienyl group under vacuum at 423 K, which leads to the formation of a well-defined mononuclear surface Fe-C(5)H(6) complex grafted to two acidic sites and one ([triple bond]Si-O-Si[triple bond]) unit, as confirmed by the lack of Fe-Fe contributions in the EXAFS spectra. Each iron atom is coordinated, on average, to three oxygen atoms of the zeolite surface with a Fe--O distance of 2.00 A and to five carbon atoms with a Fe--C distance of 2.09 A. IR spectra indicate that the cyclopentadiene-iron species grafted on the surface of the zeolite is quite stable in vacuo or under an inert or hydrogen atmosphere below 423 K, and is also relatively stable under oxygen at room temperature. However, the cyclopentadiene ligand readily reacts with CO to form a compound containing carbonyl at 323 K, and even at room temperature. The single carbonyl band in the IR spectra provides evidence for the nearly uniform formation of a cyclopentadiene-iron species on the surface of the zeolite.

Efficient decomposition of benzene over a beta-Ga2O3 photocatalyst under ambient conditions.

A porous beta-Ga2O3 photocatalyst has been successfully prepared. The photocatalyst was characterized by XRD, N2 adsorption-desorption, TEM, UV/vis, and FTIR techniques. The photocatalytic activity of the sample was evaluated by the decomposition of benzene in air under UV light illumination and was compared with that of the commercial titania (Degussa P25) and Pt/P25. Results revealed that the synthesized Ga2O3 was porous beta-Ga2O3 and was highly photoactive for mineralizing benzene and its derivatives (e.g., toluene and ethylbenzene) to CO2 under ambient conditions. The photocatalytic conversion of benzene over beta-Ga2O3 was about 1 order of magnitude higher than that over P25, and no obvious deactivation of beta-Ga2O3 was observed during the prolonged operation of 80 h. The high activity and long-term stability of the Ga2O3 have been ascribed to its stronger oxidative capability and higher specific surface area in comparison with P25.

[Photocatalytic removing of a mustard gas analogue 2-CEES vapor over SO4(2-)/TiO2].

Disinfection with photocatalysis, compared to with the conventional cleanout, is both high efficient and non contaminative, but the simple TiO2 photocatalyst is showing to be of low activity and low active stability so to be hardly practical application. In the paper, SO4(2-)/TiO2 were papered by surface modification of TiO2 with dilute H2SO4, and the photocatalytic degradation of 2-chloroethyl ethyl sulfide (2-CEES) on the samples was examined in a fixed-bed microreactor. The examination show that the acidic modification enhanced both the activity and the active stability of TiO2, and the sample ST200 prepared by calcination at 200 degrees C was better than ST400 by calcination at 400 degrees C. The effect of water vapor content and reaction temperature on the photocatalytic degradation of 2-CEES was also tested, showing that the sample ST200 had high activity and stability at 90 degrees C, and kept a constant activity when adding 30.5 mL/L water vapor into the reactive system in which 2-CEES initial concentration was low to < 61 microL x L(-1). In addition, it was found that supporting SO4(2-)/TiO2 on gamma-Al2O3, SiO2 and active carbon could improve on the activity and stability of SO4(2-)/TiO2, and on supports SiO2 is the best one.

[Photocatalytic functional ceramic and its speciality of photodecomposition].

Photocatalytic ceramic was prepared by coating photocatalytic membrane on ceramic matrix. The photocatalytic behavior of the TiO2 coated ceramic for degradation of oleic acid, ethylene, SO2, NOx and sterilization was studied by using XRD, chromatogram, in-situ IR and spectrophotometer. The results showed that the photocatalytic ceramic prepared by special conditions have the function of environmental conservation such as the photodegradating organic contaminants, removing inorganic baleful gas and killing bacteria. Degradation ratio of ethylene, oleic acid, SO2 and NOx reached 95%-100% respectively for the photocatalytic functional ceramic.

H2-O2 atmosphere increases the activity of Pt/TiO2 for benzene photocatalytic oxidation by two orders of magnitude.

Unprecedented photocatalytic activity and durability of Pt/TiO(2) for decomposing persistent organic pollutants (e.g. benzene) have been obtained by adding trace H(2) into an O(2)-rich photooxidation system.

Magnetic field effect on photocatalytic degradation of benzene over Pt/TiO2.

The magnetic field effect on heterogeneous photocatalytic degradation of benzene over Pt/TiO2 has been observed for the first time. The coupling effect between magnetic field and photo field influences the conversion of benzene and production of CO2 in different modes.