Determination of triapine,a ribonucleotide reductase inhibitor,in human plasma by liquid chromatography tandem mass spectrometry

Triapine is an inhibitor of ribonucleotide reductase (RNR). Studies have shown that triapine significantly decreases the activity of RNR and enhanced the radiation‐mediated cytotoxicity in cervical and colon cancer. In this work, we have developed and validated a selective and sensitive LC‐MS/MS method for the determination of triapine in human plasma. In this method, 2‐[(3‐fluoro‐2‐pyridinyl)methylene] hydrazinecarbothioamide (NSC 266749) was used as the internal standard (IS); plasma samples were prepared by deproteinization with acetonitrile; tripaine and the IS were separated on a Waters Xbridge Shield RP₁₈ column (3.5 µm; 2.1 × 50 mm) using a mobile phase containing 25.0% methanol and 75.0% ammonium bicarbonate buffer (10.0 mm , pH 8.50; v/v); column eluate was monitored by positive turbo‐ionspray tandem mass spectrometry; and quantitation of triapine was carried out in multiple‐reaction‐monitoring mode. The method developed had a linear calibration range of 0.250–50.0 ng/mL with correlation coefficient of 0.999 for triapine in human plasma. The IS‐normalized recovery and the IS‐normalized matrix factor of triapine were 101–104% and 0.89–1.05, respectively. The accuracy expressed as percentage error and precision expressed as coefficient of variation were ≤±6 and ≤8%, respectively. The validated LC‐MS/MS method was applied to the measurement of triapine in patient samples from a phase I clinical trial. Copyright © 2015 John Wiley & Sons, Ltd.     

Feasible Tuning of Surface OVs on (001) TiO2 for Superior Photocatalytic Nitrogen Fixation Activity

A feasible tuning method for oxygen vacancies was realized by annealing under 3 atm H₂ with (001)-exposed TiO₂ nanosheets. The colored TiO₂ sample exhibits an excellent N₂ photo-fixation rate owing to the abundant oxygen vacancies (OVs) thus demonstrating that annealing with high pressure H₂ is exceedingly efficient for tuning surface OVs.     

Remote Fluorination and Fluoroalkyl(thiol)ation Reactions

Remote functionalization reactions have the power to transform a C−H (or C−C) bond at a distant position from a functional group. This Review summarizes recent advances and key breakthroughs in remote fluorination, trifluoromethylation, difluoromethylation, trifluoromethylthiolation, and fluoroalkenylation reactions. Several powerful strategies have emerged to control the reactivity and distal selectivity such as the undirected radical approach, the 1,5-hydrogen atom transfer, the metal migration, the use of distant directing groups, and the ring-opening reactions. These unconventional and predictable C−H (and C−C) functionalization transformations should allow for the preparation of a wide range of otherwise-difficult-to-access alkyl, aromatic, heteroaromatic, and structurally complex fluorides.     

Two novel d10 transition metal complexes based on 1H‐benzimidazole‐5,6‐dicarboxylic acid: Synthesis,structure and multifunctional luminescence detection

Two new coordination complexes based on benzimidazole dicarboxylic acid, Zn(Hbidc)?H₂O ( 1 ) and Cd(Hbidc)(H₂O) ( 2 ), have been synthesized under hydrothermal conditions. The complexes were characterized using elemental analysis, infrared and UV–visible spectroscopies, powder X‐ray diffraction, thermogravimetry and single‐crystal X‐ray diffraction. Structural analyses showed that the crystal structures of 1 and 2 are different, due to the various modes of linking of the benzimidazole dicarboxylic acid. Complex 1 has a two‐dimensional network structure and 2 has a three‐dimensional network structure. In addition, we studied the performance of the fluorescence response of two complexes. Results showed that the complexes can be used as chemical sensors for multifunctional testing, such as for UO₂²⁺, xanthine and Fe³⁺ ions. Even if the concentration is very low, they could also be detected, showing that coordination complexes 1 and 2 have very high fluorescence sensitivity. The detection limit for UO₂²⁺ is 5.42 nM ( 1 ) and 0.02 nM ( 2 ), that for xanthine is 1.37 nM ( 1 ) and 0.28 nM ( 2 ), and that for Fe³⁺ ions is 0.76 nM ( 1 ) and 0.62 nM ( 2 ).     

Ultrathin Mn Doped Ni-MOF Nanosheet Array for Highly Capacitive and Stable Asymmetric Supercapacitor

In this study, we demonstrate that an Mn-doped ultrathin Ni-MOF nanosheet array on nickel foam (Mn_0.1-Ni-MOF/NF) serves as a highly capacitive and stable supercapacitor positive electrode. The Mn_0.1-Ni-MOF/NF shows an areal capacity of 6.48 C cm⁻² (specific capacity C: 1178 C g⁻¹) at 2 mA cm⁻² in 6.0 m KOH, outperforming most reported MOF-based materials. More importantly, it possesses excellent cycle stability to maintain 80.6 % capacity after 5000 cycles. An asymmetric supercapacitor device utilizing Mn_0.1-Ni-MOF/NF as the positive electrode and activated carbon as the negative electrode attains a high energy density of 39.6 Wh kg⁻¹ at 143.8 Wkg⁻¹ power density with a capacitance retention of 83.6 % after 5000 cycles.     

Comparison of efficiency calibration techniques of HPGe detector for radioactivity measurement of soil sample in Marinelli geometry

Journal of Radioanalytical and Nuclear Chemistry - To keep the accredited category for the gamma spectrometry test in our laboratory, the efficiency curves of a HPGe detector for soil sample in...     

Investigation of the interaction between protein and europium doped polymer

The interactions between bovine serum albumin (BSA) and polymer (poly (METAC-co-NIPAm-co-Eu(AA)3Phen), PMNEu) containing rare earth element (Europium) were detailedly investigated by both of experimental techniques, such as fluorescence spectroscopic analysis, zeta-potential characterization, hydrodynamic size measurements and transmission electron microscopy (TEM) observation, and theoretical calculations. As a result, we concluded that PMNEu could interact with BSA through electrostatic force and quench the fluorescence of BSA, which was regarded as the static quenching mechanism. In addition, the binding constant and binding sites number of BSA with PMNEu were calculated, and the distance between PMNEu and BSA was also estimated to be 1.9?nm based on Föster’s theory. Furthermore, the two fluorescence peaks of PMNEu at 594?nm and 618?nm were detected, and the density of them increased with the more BSA being added to couple with PMNEu. Additionally, The zeta-potential results confirmed the electrostatic interaction mode between BSA and PMNEu, which was concluded with the previous thermodynamic analysis. At last, the results from the hydrodynamic size measurement had a good agreement with those from the TEM observation about the structure and size variation during the complexation of PMNEu with different concentrations of BSA.     

Multiple positive solutions for Schrödinger‐Poisson system involving singularity and critical exponent

In this paper, the existence and multiplicity of positive solutions is established for Schrödinger‐Poisson system of the form where 0 ∈ Ω is a smooth bounded domain in , , and λ > 0 is a real parameter. Combining with the variational method and Nehari manifold method, two positive solutions of the system are obtained.     

In-situ cation exchange enhances room temperature phosphorescence of a family of metal-organic frameworks

The rational designability and chemical tunability of metal-organic frameworks(MOFs)are enabling tributes to efficaciously enhance their room temperature phosphorescence(RTP)performance.A family of stable anionic MOFs,[Zn₂(4,5-ImDC)₂]M₂(NKU-132,M=(CH₃)₂NH₂or(CH₂CH₃)₂NH₂),featuring significant RTP have been synthesized.By rational cation selection and in-situ replacement from dimethylammonium to diethylammonium,the phosphorescence lifetime is increased from 30.88 to126.3 ms,along with less sensitivity to air.This work provides an anti-quenching and lifetime tuning example for RTP-MOFmaterials via facile host-guest chemistry.     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.