Surface-Induced Keto-Enol Tautomerization of DNA Base Molecules and Consequent [4 + 2]-like Cycloaddition on Si(111)7×7.

Adsorption and film growth of deoxyribonucleic acid (DNA) base molecules (cytosine, guanine, thymine, and adenine) on Si(111)7×7 have been studied by combining X-ray photoelectron spectroscopy (XPS) with ab initio calculations based on the density functional theory (DFT). Multiple tautomeric forms and keto-enol tautomerization are revealed by the O 1s, N 1s, and C 1s XPS spectra of the O-containing DNA bases: cytosine, guanine, and thymine. While the carbonyl group-containing keto tautomer is more stable in a thick film and in powder, the hydroxyl group-containing enol tautomer is found at the interface. The keto-enol tautomerization, as induced by the reactive Si(111)7×7 surface, leads to the formation of a conjugated aromatic six-membered ring with a delocalized π electron system and to the consequent [4 + 2]-like cycloaddition between the enol tautomer and the 7×7 surface. The DFT calculation suggests that the enol tautomer exhibits a kinetic advantage over the keto one for the [4 + 2]-like cycloaddition. Among the several plausible pathways for the cycloaddition provided by the enol tautomer, the experimentally determined one involves a ring N and ring C atom (a polar pair), rather than two ring C atoms (a nonpolar pair), to better match the polar Si adatom-restatom pair of the 7×7 surface. Furthermore, the reacted ring C atom does not have any attached terminal functional group (e.g., -NH2 and -OH). Further deposition leads to continuous film growth in the keto tautomeric form for cytosine and guanine. For the only O-free DNA base molecule, adenine, dative bonding N → Si, rather than the [4 + 2]-like cycloaddition, is observed on the 7×7 surface. Of the four DNA base molecules, adenine is also the only one with its aromaticity maintained when adsorbed on the Si(111)7×7 surface. A reactive surface like the 7×7 surface could therefore provide a new control to trigger tautomerization that is often associated with genetic mutation.

V2O5-Fe3O4/rGO Ternary Nanocomposite with Dual Applications as a Dye Degradation Photocatalyst and OER Electrocatalyst.

The design and synthesis of structured nanomaterials with dual properties have always been highly attractive in various fields, especially in the reduction of environmental pollution as well as the generation of renewable energy. In this study, the synthesized ternary V2O5-Fe3O4/rGO nanocomposite was investigated to evaluate both the photocatalytic and electrocatalytic activities for the removal of methylene blue (MB) dye under UV/visible light radiation and oxygen evolution reaction (OER), respectively. The magnetized V2O5-Fe3O4/rGO nanocomposite is characterized by TEM, FE-SEM (with coupling by elemental mapping), EDS, XRD, FTIR, Raman, PL, DRS, and UV-vis analyses. The obtained results show that the graphene oxide substrate is decorated very well using Fe3O4 and V2O5 nanoparticles and converted to reduced graphene oxide (rGO). Furthermore, the V2O5-Fe3O4/rGO nanocomposite is considered as an active catalyst material to modify the commercial glassy carbon electrode for OER using linear sweep voltammetry (LSV). The photocatalytic activity of this novel nanocomposite revealed 89.2% (kobs = 1.7 × 10-2 min-1) and 76% (kobs = 8.3 × 10-3 min-1) degradation efficiencies of MB dye under UV and visible light irradiation at room temperature, respectively, and the surface area of the V2O5-Fe3O4/rGO nanocomposite was examined to be 705.8 cm2/g by N2 adsorption-desorption isotherms. In addition, electrochemical measurements determined the best OER performance of the ternary nanocomposite with the lowest overpotential (458 mV) and Tafel slope (132 mV dec-1) compared to the rGO substrate, Fe3O4, V2O5 nanoparticles, and binary nanocomposites. This work shows much enhancements in both photocatalytic and electrocatalytic activities due to the synergistic effect of the decorated GO support with V2O5 and Fe3O4 nanoparticles.

Crystallization Retardation and Synergistic Trap Passivation in Perovskite Solar Cells Incorporated with Magnesium-Decorated Graphene Quantum Dots.

One of the encouraging strategies for enhancing the efficiency of perovskite solar cells (PSCs) is to reduce defects, trap states of pinholes, and charge recombination rate in the light absorber layer of perovskite, which can be addressed by increasing the perovskite grain size. The utilization of Mg-decorated graphene quantum dots (MGQD) or graphene quantum dots (GQDs) into a perovskite precursor solution for further crystal modification is introduced in this study. Studies on the crystalline structure and morphology of MGQD generated from GQDs demonstrate that MGQD has a greater crystal size than GQD. Therefore, higher light absorption in the whole UV-vis spectrum and a larger grain size for the perovskite/MGQD layer compared to the perovskite/GQD sample are achieved. Moreover, more photoluminescence peak quenching of perovskite/MGQD and extended carrier recombination lifetime (from 3 to 40 ns) verify the surface and grain boundary trap passivation compared to pristine perovskite. Consequently, PSCs in an n-i-p configuration containing perovskite/MGQD show a higher performance of 10.2% in comparison to the pristine perovskite at 7.2%, attributed to the enhanced JSC from 13.2 to 19.1 mA cm-2. Thus, incorporating MGQDs into the perovskite layer is a hopeful approach for obtaining a superior perovskite film with impressive charge extraction and decreased nonradiative charge recombination.

Controlled synthesis of mixed molecular nanostructures from folate and deferrioxamine-Ga(III) on gold and tuning their performance for cancer cells.

A new strategy is developed for construction of the mixed molecular nanostructures from folic acid (FOA), a targeting agent, and deferrioxamoine-Ga(III), (DFO-Ga(III)), a theranostic agent, on gold-mercaptopropionic acid surface, Au-MPA. The strategy is focused to achieve a system in which all the active constituents of FOA; i.e., pteridine rings, p-aminobenzoeic acid, and the glutamic acid, having high affinity for folate receptor overexpressed on cancer cells; remain unreacted in adjacent to DFO-Ga(III), Au-MPA-[DFO-Ga(III)]‖-[FOA]. For this purpose, the NH2 groups of FOA and DFO-Ga(III) were attached covalently and separately to COOH of Au-MPA surface allowing all the active groups of FOA to be available for drug delivery purposes. The data obtained through several electrochemical and surface analysis techniques, supported successful construction of the designed mixed molecular nanostructures system. In addition, the results showed that the system is stable, and Ga(III) ion does not leave DFO-Ga(III) complex. The prepared surface was successfully tested for capturing of the breast cancer cells 4T1 as a model. The measurements showed a rapid uptake kinetics (t1/2 of ~6.0min) and efficient accessibility of the system by the cancer cells; the Rct was significantly increased in the presence of 4T1 cells compared with blank PBS (ΔRct ~420kΩ).

Immobilization of methotrexate anticancer drug onto the graphene surface and interaction with calf thymus DNA and 4T1 cancer cells.

Immobilization of methotrexate (MTX) anticancer drug onto the graphene surface is reported through three methods, including either covalent linkage via (a) EDC/NHS organic activators and (b) electrografting of MTX diazonium salt, or (c) noncovalent bonding, resulting in three different systems. To evaluate the interaction ability of the immobilized MTX with biological species, calf thymus DNA (ctDNA), mouse 4T1 breast tumor, and Human foreskin fibroblast (hFF) cells as models of the primary intracellular target of anticancer drugs, cancer and normal cells, respectively, are examined. The features of the constructed systems and their interactions with ctDNA are followed by surface analysis techniques and electrochemical methods. The results indicate that (i) the amount of the immobilized MTX on the graphene surface is affected by type of the immobilization method; and a maximum value of (Γ=9.3±0.9pmolcm-2) is found via electrografting method, (ii) graphene-modified-MTX has high affinity for ctDNA in a wide dynamic range of concentrations, and (iii) the nature of the interaction is of electrostatic and/or hydrogen bonding type, formed most probably between OH, NH and CO groups of MTX and different DNA functions. Finally, electrochemical impedance spectroscopy results approved the high affinity of the systems for 4T1 cancer cells.