Simulation of oxidative stress of guanosine and 8-oxo-7,8-dihydroguanosine by electrochemically assisted injection–capillary electrophoresis–mass spectrometry

Oxidative stress plays a crucial role in DNA and RNA damage within biological cells. As a consequence, mutations of DNA can occur, leading to disorders like cancer and neurodegenerative and cardiovascular diseases. The oxidative attack of guanosine and 8-oxo-7,8-dihydroguanosine is simulated by electrochemistry coupled to capillary electrophoresis–mass spectrometry. The electrochemical conversion of the compound of interest is implemented in the injection protocol termed electrochemically assisted injection (EAI). In this way, oxidation products of guanosine can be generated electrochemically, separated by capillary electrophoresis, and detected by electrospray ionization time-of-flight mass spectrometry (EAI–CE–MS). A fully automated laboratory-made EAI cell with an integrated buffer reservoir and a compartment holding screen-printed electrodes is used for the injection. In this study, parameters like pH of the sample solution and the redox potential applied during the injection were investigated in terms of corresponding formation of well-known markers of DNA damage. The important product species, 8-oxo-7,8-dihydroguanosine, was investigated in a separate study to distinguish between primary and secondary oxidation products. A comparison of product species formed under alkaline, neutral, and acidic conditions is presented. To compare real biological systems with an analytical approach for simulation of oxidative stress, it is desirable to have a well-defined control over the redox potential and to use solutions, which are close to physiological conditions. In contrast to typical HPLC–MS protocols, the hyphenation of EAI, CE, and MS enables the generation and separation of species involved without the use of organic solvents. Thus, information of the electrochemical behavior of the nucleoside guanosine as well as the primary oxidation product 8-oxo-7,8-dihydroguanosine can be characterized under conditions close to the physiological situation. In addition, the migration behavior found in CE separations of product species can be used to identify compounds if several possible species have the same mass-to-charge values determined by MS detection.

Open image in new window

Figure ?

     

Novel Red Phosphorescent Polymers Bearing Both Ambipolar and Functionalized IrIII Phosphorescent Moieties for Highly Efficient Organic Light‐Emitting Diodes

A series of novel red phosphorescent polymers is successfully developed through Suzuki cross‐coupling among ambipolar units, functionalized Ir^III phosphorescent blocks, and fluorene‐based silane moieties. The photophysical and electrochemical investigations indicate not only highly efficient energy‐transfer from the organic segments to the phosphorescent units in the polymer backbone but also the ambipolar character of the copolymers. Benefiting from all these merits, the phosphorescent polymers can furnish organic light‐emitting diodes (OLEDs) with exceptional high electroluminescent (EL) efficiencies with a current efficiency (η _L) of 8.31 cd A⁻¹, external quantum efficiency (η _ext) of 16.07%, and power efficiency (η _P) of 2.95 lm W⁻¹, representing the state‐of‐the‐art electroluminescent performances ever achieved by red phosphorescent polymers. This work here might represent a new pathway to design and synthesize highly efficient phosphorescent polymers.

     

Intramolecular enantiomerism as revealed from Raman optical activity spectrum

An algorithm is employed to retrieve the differential bond polarizabilities (DBP) of the C‐C bonds from the Raman optical activity spectrum of (‐)β‐pinene. (‐)β‐pinene possesses two stereo centers (chiral centers) and a local mirror reflection that interchanges the S type part and R type part in one molecular. It is demonstrated that this local mirror reflection could induce an approximate (or symmetry breaking) mirror reflection that reverses the signs of the DBP of the pair bond coordinates that are related to each other by the mirror reflection.This can be called intramolecular enantiomerism (IE). More cases of IE are discussed by the analysis of (‐)α‐pinene, (R)‐(+)‐4‐isopropyl‐1‐methylcyclohexene and (R)‐(+)‐3‐methylcyclohexanone together with previously studied limonene case. Copyright © 2015 John Wiley & Sons, Ltd.     

Photonic Floquet topological insulators in atomic ensembles

The feasibility of realizing a photonic Floquet topological insulator (PFTI) in an atomic ensemble is demonstrated. The interference of three coupling fields will split energy levels periodically, to form a periodic refractive index structure with honeycomb profile that can be adjusted by different frequency detunings and intensities of the coupling fields. This in turn will affect the appearance of Dirac cones in momentum space. When the honeycomb lattice sites are helically ordered along the propagation direction, gaps open at Dirac points, and one obtains a PFTI in an atomic vapor. An obliquely incident beam will be able to move along the zigzag edge of the lattice without scattering energy into the PFTI, due to the confinement of edge states. The appearance of Dirac cones and the formation of a photonic Floquet topological insulator can be shut down by the third‐order nonlinear susceptibility and opened up by the fifth‐order one.

     

Rapid and efficient column separation of Re(VII) as a surrogate for Tc(VII) with benzimidazole-based cross-linked poly(ionic liquid)s

Journal of Radioanalytical and Nuclear Chemistry - In this study, the imidazole-based poly(ionic liquid)s (PILs) synthesized by one step method has been applied for the enrichment and recovery of...     

Secondary Metabolites of Clinacanthus nutans

Chemistry of Natural Compounds -     

Investigation on the Interaction of Dy(Ш)/Rutin Complexes with Bovine Serum Albumin by Spectroscopic Methods

Journal of Solution Chemistry - The interaction between Dy(Ш)/Rutin complexes and bovine serum albumin (BSA) was studied by fluorescence, ultraviolet (UV) absorption, three-dimensional...     

Nonflammable nonaqueous electrolytes for lithium batteries

As the energy density of state-of-the-art lithium (Li)-ion batteries (LIBs) increases, the safety concern of LIBs using liquid electrolytes is drawing increasing attention. Flammability of electrolytes is a critical link of the overall safety performance of LIBs and Li metal batteries. For this reason, intensive efforts have been devoted to suppressing the flammability of liquid electrolytes. In this short review, the common approaches to reduce the flammability of the nonaqueous liquid electrolytes will be summarized. The advantages and limitations of these approaches will also be discussed.     

Advances in nucleic acid architectures for electrochemical sensing

Nucleic acid–based electrochemical sensors are ideally suited to the detection of molecular targets for which enzymatic detection or direct electrochemical oxidation – reduction reactions are not possible. Moreover, the versatility of nucleic acids in their ability to bind a great variety of target types, from small molecules to single-entity mesoscopic targets, makes them attractive receptors for the development of electrochemical biosensors. In this brief opinion piece, we discuss field advances from the past two years. We hope the works highlighted here will inspire the community to pursue creative designs enabling the detection of larger and more complex targets with a specific focus on analytical validation and translation into preclinical or clinical applications.     

Two New Aristolochic Acid Analogues from the Roots of Aristolochia contorta with Significant Cytotoxic Activity

Twelve compounds, including two new aristolochic acid analogues with a formyloxy moiety (9–10) and 10 known aristolochic acid derivates (1–8 and 11–12), were obtained from the roots of Aristolochia contorta. Their structures were elucidated using extensive spectroscopic methods. Their cytotoxic activity in human proximal tubular cells HK-2 was evaluated by the MTT method, which has been widely used to assess cell viability. Among these molecules, compounds 3 and 9 were found to be more cytotoxic. Furthermore, molecular modeling was used to evaluate, for the first time, the interactions of compounds 3 and 9 with the target protein organic anionic transporter 1 (OAT1) that plays a key role in mediating aristolochic acid nephropathy. Structure–activity relationships are briefly discussed.