Zheng, Y., Hunting, D. J., Ayotte, P. and Sanche, L. Radiosensitization of DNA by Gold Nanoparticles Irradiated with High-Energy Electrons. Radiat. Res. 168, 19-27 (2008). Thin films of pGEM-3Zf(-) plasmid DNA were bombarded by 60 keV electrons with and without gold nanoparticles. DNA single- and double-strand breaks (SSBs and DSBs) were measured by agarose gel electrophoresis. From transmission electron micrographs, the gold nanoparticles were found to be closely linked to DNA scaffolds, probably as a result of electrostatic binding. The probabilities for formation of SSBs and DSBs from exposure of 1:1 and 2:1 gold nanoparticle:plasmid mixtures to fast electrons increase by a factor of about 2.5 compared to neat DNA samples. For monolayer DNA adsorbed on a thick gold substrate, the damage increases by an order of magnitude. The results suggest that the enhancement of radiosensitivity is due to the production of additional low-energy secondary electrons caused by the increased absorption of ionizing radiation energy by the metal, in the form of gold nanoparticles or of a thick gold substrate. Since short-range low-energy secondary electrons are produced in large amounts by any type of ionizing radiation, and since on average only one gold nanoparticle per DNA molecule is needed to increase damage considerably, targeting the DNA of cancer cells with gold nanoparticles may offer a novel approach that is generally applicable to radiotherapy treatments.

The electroreduction reaction of CO₂ (ECO₂RR) requires high-performance catalysts to convert CO₂ into useful chemicals. Transition metal-based atomically dispersed catalysts are promising for the high selectivity and activity in ECO₂RR. This work presents a series of atomically dispersed Co, Fe bimetallic catalysts by carbonizing the Fe-introduced Co-zeolitic-imidazolate-framework (C–Fe–Co–ZIF) for the syngas generation from ECO₂RR. The synergistic effect of the bimetallic catalyst promotes CO production. Compared to the pure C–Co–ZIF, C–Fe–Co–ZIF facilitates CO production with a CO Faradaic efficiency (FE) boost of 10%, with optimal FE_CO of 51.9%, FE_H2 of 42.4% at − 0.55 V, and CO current density of 8.0 mA cm⁻² at − 0.7 V versus reversible hydrogen electrode (RHE). The H₂/CO ratio is tunable from 0.8 to 4.2 in a wide potential window of − 0.35 to − 0.8 V versus RHE. The total FE_CO+H2 maintains as high as 93% over 10 h. The proper adding amount of Fe could increase the number of active sites and create mild distortions for the nanoscopic environments of Co and Fe, which is essential for the enhancement of the CO production in ECO₂RR. The positive impacts of Cu–Co and Ni–Co bimetallic catalysts demonstrate the versatility and potential application of the bimetallic strategy for ECO₂RR.

Four different gold nanoparticle (GNP) preparations, including naked GNPs and GNPs coated either with thiolated undecane (S-C(11)H(23)), or with dithiolated diethylenetriaminepentaacetic (DTDTPA) or gadolinium (Gd) DTDTPA chelating agents, were synthesized. The average diameters, for each type of nanoparticle, are 5 nm, 10 and 13 nm, respectively. Dry films of plasmid DNA pGEM-3Zf(-), DNA with bound GNPs and DNA with coated GNPs were bombarded with 60 keV electrons. The yields of single and double strand breaks were measured as a function of exposure by electrophoresis. The binding of just one GNP without coating to DNA containing 3197 base pairs increases single and double strand breaks by a factor of 2.3 while for GNPs coated with S-C(11)H(23) this factor is reduced to 1.6. The GNPs coated with DTDTPA and DTDTPA:Gd in the same ratio with the DNA, produce essentially no increment in damage. These results could be explained by the attenuation by the coatings of the intensity of the low-energy photoelectrons emitted from the GNPs. Thus, coatings of GNPs may considerably attenuate the short-range low-energy electrons emitted from gold, leading to a considerable decrease of radiosensitization. According to our results, the highest radiosensitization should be obtained with GNPs having the shortest possible ligand, directed to the DNA of cancer cells.

Gold nanoparticles (GNP) passivated by dithiolated diethylenetriaminepentaacetic (DTDTPA) linkers, GNP@DTDTPA, have been synthesized. The well-defined ZnO nanocomposite (GNP@DTDTPA/ZnO) functionalized by GNP@DTDTPA was prepared via a facile and green self-assembly approach. The specific interaction mechanism responsible for the self-assembly motif was elucidated by XPS, zeta potential and FTIR analysis. The self-assembly process was established primarily by a large amount of polar functional groups such as carboxyl (COOH), carbonyl (CO), and amide (NH–CO) groups in the DTDTPA profile, which impels GNP@DTDTPA to bind intrinsically with hydroxyl groups on the ZnO surface through hydrogen bonding interactions. On the other hand, the attractive electrostatic force between the negatively charged GNP@DTDTPA and the positively charged ZnO surface also contributes to the monodispersivity of GNP@DTDTPA on the ZnO support. The GNP/ZnO obtained after calcination of GNP@DTDTPA/ZnO retains the mono-distribution of GNP and exhibits more enhanced photocatalytic and photoelectrochemical performances compared to pure ZnO. We propose a possible mechanism that the well-distributed GNP could serve as an “electron reservoir” and improve the separation efficiency of photogenerated electron–hole pairs. This method could provide a simple and straightforward approach for achieving a uniform distribution of noble-metal nanoparticles on the surface of semiconductors for versatile photocatalytic and photoelectrochemical applications.

Thin molecular films of the short single strand of DNA, GCAT, were bombarded under vacuum by electrons with energies between 4 and 15 eV. Ex vacuo analysis by high-pressure liquid chromatography of the samples exposed to the electron beam revealed the formation of a multitude of products. Among these, 12 fragments of GCAT were identified by comparison with reference compounds and their yields were measured as a function of electron energy. For all energies, scission of the backbone gave nonmodified fragments containing a terminal phosphate, with negligible amounts of fragments without the phosphate group. This indicates that phosphodiester bond cleavage by 4–15 eV electrons involves cleavage of the C–O bond rather than the P–O bond. The yield functions exhibit maxima at 6 and 10–12 eV, which are interpreted as due to the formation of transient anions leading to fragmentation. Below 15 eV, these resonances dominate bond dissociation processes. All four nonmodified bases are released from the tetramer, by cleavage of the N-glycosidic bond, which occurs principally via the formation of core-excited resonances located around 6 and 10 eV. The formation of the other nonmodified products leading to cleavage of the phosphodiester bond is suggested to occur principally via two different mechanisms: (1) the formation of a core-excited resonance on the phosphate unit followed by dissociation of the transient anion and (2) dissociation of the CO bond of the phosphate group formed by resonance electron transfer from the bases. In each case, phosphodiester bond cleavage leads chiefly to the formation of stable phosphate anions and sugar radicals with minimal amounts of alkoxyl anions and phosphoryl radicals.