Determination of Ubiquinone in Blood by High-Performance Liquid Chromatography with Post-Column Fluorescence Derivatization Using 2-Cyanoacetamide

It was shown that ubiquinone (CoQ₁₀) and ubiquinol (CoQ₁₀H₂) produce fluorescence products under alkaline conditions when reacted with 2-cyanoacetamide. The reaction mixture from CoQ₁₀ gave fluorescence with excitation and emission maximum wavelengths at 442 nm and 549 nm, respectively. This reaction was considered to proceed via Craven’s reaction. Moreover, 2-cyanoacetamide was shown to be a useful reagent for high-performance liquid chromatography (HPLC) with post-column fluorescence derivatization of CoQ₁₀ and CoQ₁₀H₂ in blood. CoQ₁₀ showed a linear response in the range of 0.32–1276 ng, and the detection limit (S/N = 3) was 0.16 ng. Moreover, the sample pretreatment by deproteinization and extraction of CoQ₁₀ and CoQ₁₀H₂ from plasma using 1-propanol with potassium formate was effective for excellent separation of CoQ₁₀ and CoQ₁₀H₂ from other fluorescent substances in the blood. This simple and rapid pretreatment was considered to minimize the oxidation of CoQ₁₀H₂. On the other hand, CoQ₁₀ and CoQ₁₀H₂ in plasma samples obtained by finger prick were detected, as in venous blood obtained by venipuncture. Our method involving the simple and rapid collection of plasma by finger prick and sample pretreatment is thought to be applicable for the determination of CoQ₁₀H₂/total CoQ₁₀ ratio as a biomarker of oxidative stress.     

Topological Superconductivity in Cu(x)Bi(2)Se(3)

A topological superconductor (TSC) is characterized by the topologically protected gapless surface state that is essentially an Andreev bound state consisting of Majorana fermions. While a TSC has not yet been discovered, the doped topological insulator Cu(x)Bi(2)Se(3), which superconducts below ～3 K, has been predicted to possess a topological superconducting state. We report that the point-contact spectra on the cleaved surface of superconducting Cu(x)Bi(2)Se(3) present a zero-bias conductance peak (ZBCP) which signifies unconventional superconductivity. Theoretical considerations of all possible superconducting states help us conclude that this ZBCP is due to Majorana fermions and gives evidence for a topological superconductivity in Cu(x)Bi(2)Se(3). In addition, we found an unusual pseudogap that develops below ～20 K and coexists with the topological superconducting state.     

New exact Einstein-Maxwell fields for a massless charge

New solutions of the Einstein-Maxwell equations are presented. The solutions describe the gravitational fields of a massless charge.     

The low-lying electronic excited states of NiCO

Highly correlated coupled cluster methods with single and double excitations (CSSD) and CCSD with perturbative triple excitations were used to predict molecular structures and harmonic vibrational frequencies for the electronic ground state X 1Sigma+, and for the 3Delta, 3Sigma+, 3Phi, 1 3Pi, 2 3Pi, 1Sigma+, 1Delta, and 1Pi excited states of NiCO. The X 1Sigma+ ground state's geometry is for the first time compared with the recently determined experimental structure. The adiabatic excitation energies, vertical excitation energies, and dissociation energies of these excited states are predicted. The importance of pi and sigma bonding for the Ni-C bond is discussed based on the structures of excited states.     

Characterization of singlet ground and low-lying electronic excited states of phosphaethyne and isophosphaethyne

The singlet ground ((approximate)X(1)Sigma1+) and excited (1Sigma-,1Delta) states of HCP and HPC have been systematically investigated using ab initio molecular electronic structure theory. For the ground state, geometries of the two linear stationary points have been optimized and physical properties have been predicted utilizing restricted self-consistent field theory, coupled cluster theory with single and double excitations (CCSD), CCSD with perturbative triple corrections [CCSD(T)], and CCSD with partial iterative triple excitations (CCSDT-3 and CC3). Physical properties computed for the global minimum ((approximate)X(1)Sigma+HCP) include harmonic vibrational frequencies with the cc-pV5Z CCSD(T) method of omega1=3344 cm(-1), omega2=689 cm(-1), and omega3=1298 cm(-1). Linear HPC, a stationary point of Hessian index 2, is predicted to lie 75.2 kcal mol(-1) above the global minimum HCP. The dissociation energy D0[HCP((approximate)X(1)Sigma+)-->H(2S)+CP(X2Sigma+)] of HCP is predicted to be 119.0 kcal mol(-1), which is very close to the experimental lower limit of 119.1 kcal mol(-1). Eight singlet excited states were examined and their physical properties were determined employing three equation-of-motion coupled cluster methods (EOM-CCSD, EOM-CCSDT-3, and EOM-CC3). Four stationary points were located on the lowest-lying excited state potential energy surface, 1Sigma- -->1A", with excitation energies Te of 101.4 kcal mol(-1) (1A"HCP), 104.6 kcal mol(-1)(1Sigma-HCP), 122.3 kcal mol(-1)(1A" HPC), and 171.6 kcal mol(-1)(1Sigma-HPC) at the cc-pVQZ EOM-CCSDT-3 level of theory. The physical properties of the 1A" state with a predicted bond angle of 129.5 degrees compare well with the experimentally reported first singlet state ((approximate)A1A"). The excitation energy predicted for this excitation is T0=99.4 kcal mol(-1) (34 800 cm(-1),4.31 eV), in essentially perfect agreement with the experimental value of T0=99.3 kcal mol(-1)(34 746 cm(-1),4.308 eV). For the second lowest-lying excited singlet surface, 1Delta-->1A', four stationary points were found with Te values of 111.2 kcal mol(-1) (2(1)A' HCP), 112.4 kcal mol(-1) (1Delta HPC), 125.6 kcal mol(-1)(2(1)A' HCP), and 177.8 kcal mol(-1)(1Delta HPC). The predicted CP bond length and frequencies of the 2(1)A' state with a bond angle of 89.8 degrees (1.707 A, 666 and 979 cm(-1)) compare reasonably well with those for the experimentally reported (approximate)C(1)A' state (1.69 A, 615 and 969 cm(-1)). However, the excitation energy and bond angle do not agree well: theoretical values of 108.7 kcal mol(-1) and 89.8 degrees versus experimental values of 115.1 kcal mol(-1) and 113 degrees. of 115.1 kcal mol(-1) and 113 degrees.