A Bracketing Method For Proton Affinity Measurements Of Dehydro-And Didehydropyridines,
2015
Purdue University
A Bracketing Method For Proton Affinity Measurements Of Dehydro-And Didehydropyridines, Guannan Li
Open Access Theses
Proton affinity (PA) is a fundamental property that is related to the structure and reactivity of a molecule. Currently, very few experimental PA values are available for organic radicals and none for biradicals. Equilibrium methods cannot be used for these measurements. The traditional bracketing method is based on monitoring reactions of different reference bases with known proton affinities with the protonated analyte for the occurrence of exothermic proton transfer to determine the upper and lower limits of proton affinity. However, the energy deposited into the precursor ions upon CAD when forming protonated radicals may cause endothermic proton transfer reactions occur …
Quantification Of Molecular Aggregation Equilibria Using Spectroscopic Measurements And Random Mixing Modeling,
2015
Purdue University
Quantification Of Molecular Aggregation Equilibria Using Spectroscopic Measurements And Random Mixing Modeling, Blake M. Rankin
Open Access Dissertations
Molecular aggregation equilibria, such as the binding of ligands to a central solute molecule, are prevalent throughout biological processes and energy storage devices. However, both the sign and magnitude of hydrophobic and ionic interactions remains a subject of theoretical debate, and has yet to be experimentally determined. Here, Raman vibrational spectroscopy is combined with multivariate curve resolution (Raman-MCR) to experimentally quantify both the number of hydrophobic contacts between alcohol molecules in water and the affinity of ions for molecular hydrophobic interfaces. Furthermore, a generalized theoretical model is developed based on random statistics in which it is assumed that the concentration …
Mass Spectrometric Characterization Of Peptide Radical Ions And Implication For Radical Chemistry,
2015
Purdue University
Mass Spectrometric Characterization Of Peptide Radical Ions And Implication For Radical Chemistry, Lei Tan
Open Access Dissertations
Gas-phase radical ion chemistry has attracted increasing research interest from the mass spectrometry (MS) society because it provides new capabilities in bio-analysis which often complements traditional MS methods developed from even-electron ions. Fundamental studies of biomolecule related radical species are essential to broadening the scope of radical chemistry and pushing the frontiers of its analytical applications. This dissertation mainly discusses the gas-phase chemistry of peptide sulfinyl radicals (-SO·), which has been rarely studied before. In order to establish an effective research approach, a method that can generate site-specific peptide sulfinyl radical ion has been developed. This method is based on …
Optical Laser-Induced Co Desorption From Ru(0001) Monitored With A Free-Electron X-Ray Laser: Dft Prediction And X-Ray Confirmation Of A Precursor State,
2015
Stockholm University
Optical Laser-Induced Co Desorption From Ru(0001) Monitored With A Free-Electron X-Ray Laser: Dft Prediction And X-Ray Confirmation Of A Precursor State, H. Öberg, J. Gladh, M. Dell'angela, T. Anniyev, M. Beye, R. Coffee, A. Föhlisch, T. Katayama, S. Kaya, Jerry L. Larue, A. Møgelhøj, D. Nordlund, H. Ogasawara, W. F. Schlotter, J. A. Sellberg, F. Sorgenfrei, J. J. Turner, M. Wolf, W. Wurth, H. Öström, A. Nilsson, J. K. Nørskov, L. G. M. Pettersson
Biology, Chemistry, and Environmental Sciences Faculty Articles and Research
We present density functional theory modeling of time-resolved optical pump/X-ray spectroscopic probe data of CO desorption from Ru(0001). The BEEF van der Waals functional predicts a weakly bound state as a precursor to desorption. The optical pump leads to a near-instantaneous (< 100 fs) increase of the electronic temperature to nearly 7000 K. The temperature evolution and energy transfer between electrons, substrate phonons and adsorbate is described by the two-temperature model and found to equilibrate on a timescale of a few picoseconds to an elevated local temperature of ~ 2000 K. Estimating the free energy based on the computed potential of mean force along the desorption path, we find an entropic barrier to desorption (and by time-reversal also to adsorption). This entropic barrier separates the chemisorbed and precursor states, and becomes significant at the elevated temperature of the experiment (~ 1.4 eV at 2000 K). Experimental pump-probe X-ray absorption/X-ray emission spectroscopy indicates population of a precursor state to desorption upon laser-excitation of the system (Dell'Angela et al., 2013). Computing spectra along the desorption path confirms the picture of a weakly bound transient state arising from ultrafast heating of the metal substrate.
Electrochemical Monitoring Of Cell Wall-Regulated Transient Extracellular Oxidative Burst From Single Plant Cells,
2015
Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China;
Electrochemical Monitoring Of Cell Wall-Regulated Transient Extracellular Oxidative Burst From Single Plant Cells, Jun-Tao Liu, Yan-Ling Liu, Zhi Cheng, Shi-Jing Chen, Wei-Hua Huang
Journal of Electrochemistry
Oxidative burst by rapid, transient generation of reactive oxygen species (ROS) is a fundamental process for plant disease defense and signal transduction. ROS can be protective or toxic depending on their concentrations, and critical balance between ROS production and scavenging is regulated by complex and perfect mechanisms in plant cells. However, the process of rapid and transient ROS burst from plant cells and their regulatory mechanisms are far from being completely understood, owing to the methodological obstacles in real-time monitoring such a fast process. In this work, we showed the application of microelectrode electrochemistry with high spatiotemporal resolution to monitor …
Novel Dna Electrochemical Biosensor For K-Ras Point Mutation Detection Based On Dna Polymerase I,
2015
Faculty of Pharmacy, Fujian Medical University, Fuzhou 350004, China;
Novel Dna Electrochemical Biosensor For K-Ras Point Mutation Detection Based On Dna Polymerase I, Li-Qing Lin, Cheng-Fei Zhao, Zhou-Qian Jiang, Shao-Huang Weng, Xiao-Lan Xie, Xin-Hua Lin
Journal of Electrochemistry
In this article, we developed a novel DNA electrochemical sensor for obtaining a current-time curve based on DNA polymerase I. The capture probes were fixed on the Au electrode by Au interacting with -SH, and then hybridized with the K-ras mutant target DNA as far as one base before the mutation site. After hybridizing the K-ras mutant or wild target DNA, the resulting assembly reacted with the dUTP-biotin in the presence of DNA polymerase I. Then avidin-HRP combined the dUTP-biotin on the electrode. The proposed electrode was applied for detection in TMB solution by electrochemical technology. The experimental results showed …
A Novel Nitrite Sensing Electrode Based On Au/Fe3O4/Chitosan Nanocomposite,
2015
Institute of Environmental and Analytical Sciences, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, Henan, China;
A Novel Nitrite Sensing Electrode Based On Au/Fe3O4/Chitosan Nanocomposite, Ying Dong, Yong Wang, Huan-Huan Xing, Jian-Ying Qu
Journal of Electrochemistry
A novel nitrite sensing electrode based on gold nanoparticles and iron oxides (Fe3O4) magnetic nanoparticles was fabricated with chitosan as the protective film on glassy carbon matrix. Experiment results showed that the sensing electrode exhibited good electrocatalytic activity toward oxidation of nitrite, and the oxidation peak current increased linearly with the concentration of nitrite varying from 5.0×10-6 to 2.0×10-3 mol·L-1 (R=0.9996) with a detection limit of 7.1×10-7 mol·L-1 (S/N=3). The sensing electrode exhibited good sensitivity, selectivity and repeatability.
Electrochemiluminescence Assay Based On Bipolar Electrode For Bioanalysis,
2015
State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China;Department of Chemistry, College of Science, Nanjing Agricultural University, Nanjing 210095, China;
Electrochemiluminescence Assay Based On Bipolar Electrode For Bioanalysis, Mei-Sheng Wu, Jing-Juan Xu, Hong-Yuan Chen
Journal of Electrochemistry
Bipolar electrodes (BPEs) are electronic conductors which are usually embedded into microchannels. The potential difference at the BPE/solution interface is obtained by applying a voltage at the two ends of the microchannel. When it reaches a critical value, the redox reaction takes place at both poles of the BPE simultaneously. Compared with other detection methods, the electrochemiluminescence (ECL) platform based on BPE possesses the advantages of concentration enrichment, high sensitivity, low cost, portable sensor system, no need for a light source, which is quite suitable for bioanalysis. This paper reviews the ECL-BPE strategy for bioanalysis and proposes the future research …
Electrochemiluminescence Biosensors Based On The Signal Amplification Of Co-Reactants,
2015
College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China;
Electrochemiluminescence Biosensors Based On The Signal Amplification Of Co-Reactants, Hai-Jun Wang, Li-Juan Xiao, Ying He, Xin-Ya Jiang, Ya-Li Yuan, Ying Zhuo, Ya-Qin Chai, Ruo Yuan
Journal of Electrochemistry
Using co-reactants to enhance the luminous efficiency of luminophores is a common, convenient and effective method in the construction of the electrochemiluminescence (ECL) biosensors. However, the different methods of introducing co-reactants in the construction of the ECL biosensors will bring different amplification effects. In this review, several signal amplification methods through co-reactants are summarized: 1) Adding the co-reactants directly into the detection solution; 2) Immobilizing the co-reactants onto the electrode surface; 3) Using enzymatic reaction to generate co-reactants in situ around the electrode surface. And then, the outlook of the ECL signal amplification strategy is proposed on those bases.
An Enzymatic Ethanol/O2 Biofuel Cell Powered By Commercial Vodka Fuel,
2015
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, the Chinese Academy of Sciences (CAS), Beijing 100190, China;School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081, China;
An Enzymatic Ethanol/O2 Biofuel Cell Powered By Commercial Vodka Fuel, Yi-Ming Yan, Lan-Qun Mao
Journal of Electrochemistry
This study demonstrates the performance of a new type alcohol/O2 biofuel cell assembled by using alcohol dehydrogenase (ADH) and bilirubin oxidase (BOD) as the biocatalysts of the bioanode and the biocathode for the bioelectrocatalytic oxidation of alcohol and reduction of oxygen, respectively. To construct the bioanode and the biocathode, single-walled carbon nanotubes (SWCNTs) were used. In the bioanode, SWCNTs were used as the supporting materials for both methylene green (MG) which was used as the electrocatalyst for the oxidation of NADH and ADH. The as-constructed MG/ADH/SWCNTs-based bioanode exhibits a good activity toward the bioelectrocatalytic oxidation of ethanol. In the …
Sensitive Detection Of Hydroxyl Radical Based On Silver-Enhanced Gold Nanoparticle Label,
2015
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha Hunan 410082, China;College of Chemistry and Pharmaceutical engineering, Nanyang Normal University, Henan Nanyang, 473061, China;
Sensitive Detection Of Hydroxyl Radical Based On Silver-Enhanced Gold Nanoparticle Label, Yan Yang, Peng Yu, Xiao-Hua Zhang, Jin-Hua Chen
Journal of Electrochemistry
A novel DNA-based electrochemical sensor has been successfully constructed for sensitive detection of hydroxyl radical (·OH) based on the silver-enhanced gold nanoparticle label. Thiolated DNA1 was firstly immobilized on the gold electrode through Au—S bonds. The ·OH generated from Fenton reaction could induce serious oxidative damage of the DNA1 layer on the electrode surface. Then DNA2-functionalized gold nanoparticles (DNA2-AuNPs) were linked on the electrode through the hybridization between DNA2 and undamaged DNA1. Based on the catalytic reduction of silver ion by AuNPs, a silver layer was formed on the surface of AuNPs. The quantitative assay of ·OH was carried out …
A Multi-Channel Electrochemical Immunosensing System With Polyhrp-Based Signal Amplification For The Detection Of Tumor Markers,
2015
Division of Physical Biology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China;
A Multi-Channel Electrochemical Immunosensing System With Polyhrp-Based Signal Amplification For The Detection Of Tumor Markers, Wang-Ping Deng, Yan-Zhi Dou, Jing Su, Lin Hao, Shi-Ping Song, Chun-Hai Fan
Journal of Electrochemistry
We have developed a multi-channel electrochemical immunosensing system for the detection of α-fetoprotein (AFP). The sensing system consisted of carbon screen-printed electrode (SPCE) arrays and polyHRP-based signal amplification probes. AFP antigens could bind to both capture antibodies immobilized on electrode arrays ant detection antibodies (anti-AFP IgG developed in rabbit). The anti-rabbit IgG conjugated to poly-horseradish peroxidase were used as a signaling probe to bind to the immuno-complex. The current signals were harvested by a home-made multi-channels electrochemical detector. AFP could be detected in the concentration ranges of 64 pg·mL-1 ~ 250 ng·mL-1. The detection limit was as …
Fabrication And Application Of Cytochrome P450 Electrochemcial Biosensor In Drug Metabolism,
2015
School of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, China;
Fabrication And Application Of Cytochrome P450 Electrochemcial Biosensor In Drug Metabolism, Xuan Xu, Ju-Sheng Lu, Song-Qin Liu
Journal of Electrochemistry
The process of drug metabolism plays an important role in drug efficacy and toxicity in vivo. Thus, the development of cheap, continent, rapid and high-throughput method for drug metabolism studies has great guiding significance for the design of new drugs, the determination of drug dosage and the detection of clinical drugs. Since the key role played by Cytochrome P450 (CYP450) in phase-I drug reaction, the constructed CYP450 enzyme biosensor can be used for the initial screening of drugs. It is found that the replacement of coenzyme NADPH with an electrode is to provide two electrons demanded in the catalytic reaction. …
Electrochemical Detection Of L-Cysteine Based On Iron Phthalocyanine/Nitrogen-Doped Graphene Modified Electrodes,
2015
Department of Chemistry, and State Key Lab of Molecular Engineering of Polymers, Fudan University, Shanghai 200433, China;
Electrochemical Detection Of L-Cysteine Based On Iron Phthalocyanine/Nitrogen-Doped Graphene Modified Electrodes, Jing-Jing Xiao, Hui-Ying Xu, Li Xu, Bao-Hong Liu
Journal of Electrochemistry
In this study, we report a facile method to develop FePc/N-G hybrid modified electrode for the detection of L-cysteine. The electrochemical sensor was characterized by cyclic voltammetry and amperometric response. The sensor exhibited a wider linear range with rapid response which has outperformed pure FePc/GCE, highlighting the important role of nitrogen doped graphene as substrate for improving the electrochemical response property.
Naio4 Oxidation Of Mussel Adhesive Protein Film And Its Corrosion Protection For Mg-1.0ca Alloy,
2015
State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry,College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
Naio4 Oxidation Of Mussel Adhesive Protein Film And Its Corrosion Protection For Mg-1.0ca Alloy, Rui-Qing Hou, Ping-Li Jiang, Shi-Gang Dong, Chang-Jian Lin
Journal of Electrochemistry
The effect of oxidation of mussel adhesive protein (Mefp-1) film on the corrosive resistance for Mg-1.0Ca alloy was investigated by scanning electron microscopy (SEM), atom force microscopy (AFM), electron probe microanalysis (EPMA), Infrared reflection absorption spectroscopy (IRAS) and electrochemical methods. The results showed that the NaIO4 induced oxidation of the pre-formed Mefp-1 film with porous morphology involved structural change of the DOPA group in the protein and resulted in a more uniform film with net-like morphology. The protein film without oxidation had an increasing resistance for the corrosion of Mg-1.0Ca alloy up to 7 days exposure. After oxidation, Epit …
Nanosized Fe2O3 On Three Dimensional Hierarchical Porous Graphene-Like Matrices As High-Performance Anode Material For Lithium Ion Batteries,
2015
State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering, Sun Yat-sen University, Guangzhou 510275, China;
Nanosized Fe2O3 On Three Dimensional Hierarchical Porous Graphene-Like Matrices As High-Performance Anode Material For Lithium Ion Batteries, Qin-Wei Zhang, Yun-Yong Li, Pei-Kang Shen
Journal of Electrochemistry
Ferric oxide (Fe2O3) as a promising anode material for lithium ion battery is due to its high theoretical capacity (1007 mAh·g-1), earth abundance and low cost. The nanosized Fe2O3 on the three dimensional hierarchical porous graphene-like network (denoted as Fe2O3-3D HPG) has been synthesized by homogeneous precipitation and heat treatment. The 3D HPG can provide a highly conductive structure in conjunction to support well contacted Fe2O3 nanoparticles, and effectively enhance the mechanical strength of the matrices during volume changes, as well as improve the …
Preparation And Properties Of Titanium Based Metal Oxide Electrodes For Ammonia Nitrogen Wastewater Treatment,
2015
Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
Preparation And Properties Of Titanium Based Metal Oxide Electrodes For Ammonia Nitrogen Wastewater Treatment, Xue Li, Meng Xue, Ling Huang, Jun-Tao Li, Shi-Gang Sun
Journal of Electrochemistry
In this paper, four types of titanium based metal oxides electrodes were prepared by thermal decomposition method: Ti/SnO2+Sb2O3, Ti/SnO2+Sb2O3/SnO2+IrO2, Ti/SnO2+Sb2O3/SnO2+RuO2, Ti/SnO2+Sb2O3/SnO2+CeO2. The XRD results show that CeO2 in Ti/SnO2+Sb2O3/SnO2+CeO2 displayed a good crystal structure, and there was no significant oxygen evolution reaction occurred after electrolytic oxidation. Compared with the other three electrodes, the Ce-doped …
Effects Of Etchants On Surface Morphologies And Electrochemical Performance Of Iro2-Mno2 Anodic Nano-Coatings,
2015
School of Material Science and Engineering, Nanchang Hangkong University, Nanchang 330063, China;
Effects Of Etchants On Surface Morphologies And Electrochemical Performance Of Iro2-Mno2 Anodic Nano-Coatings, Qing-Guo Fan, Zhi-Guo Ye, Hui-Min Meng, Chun-Min Lu
Journal of Electrochemistry
The IrO2-MnO2 anodic nano-coatings were prepared by the traditional thermal decomposition method on the different surfaces of Ti substrates pretreated by different etchants (HCl, H2SO4, C2H2O4 and HF). Surface morphologies and electrochemical performance of the Ti based IrO2-MnO2 anodic coatings were investigated by field emission scanning electron microscopy (FESEM), cyclic voltammetry (CV) and polarization techniques. Analysis showed that the denser IrO2 nano-particles with longer dimensions were obtained at the IrO2-MnO2 anodic coating surfaces on the Ti substrates etched by HF and …
"Probing The Transition State Region In Catalytic Co Oxidation On Ru" Data Files,
2015
Stockholm University
"Probing The Transition State Region In Catalytic Co Oxidation On Ru" Data Files, H. Öström, H. Öberg, H. Xin, Jerry L. Larue, M. Beye, M. Dell'angela, J. Gladh, M. L. Ng, J. A. Sellberg, S. Kaya, G. Mercurio, D. Nordlund, W. F. Schlotter, A. Föhlisch, M. Wolf, W. Wurth, M. Persson, J. K. Nørskov, F. Abild-Pedersen, H. Ogasawara, L. G. M. Pettersson, A. Nilsson
Biology, Chemistry, and Environmental Sciences Faculty Data Sets
Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on Ru initiated by an optical laser pulse. On a timescale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface allowing the reactants to collide and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond-formation between CO and O with a distribution of OC—O bond lengths close to the transition state (TS). After …
Probing The Transition State Region In Catalytic Co Oxidation On Ru,
2015
Stockholm University
Probing The Transition State Region In Catalytic Co Oxidation On Ru, H. Öström, H. Öberg, H. Xin, Jerry L. Larue, M. Beye, M. Dell'angela, J. Gladh, M. L. Ng, J. A. Sellberg, S. Kaya, G. Mercurio, D. Nordlund, M. Hantschmann, F. Hieke, D. Kühn, W. F. Schlotter, G. L. Dakovski, J. J. Turner, M. P. Minitti, A. Mitra, S. P. Moeller, A. Föhlisch, M. Wolf, W. Wurth, M. Persson, J. K. Nørskov, F. Abild-Pedersen, H. Ogasawara, L. G. M. Pettersson, A. Nilsson
Biology, Chemistry, and Environmental Sciences Faculty Articles and Research
Femtosecond x-ray laser pulses are used to probe the CO oxidation reaction on Ru initiated by an optical laser pulse. On a timescale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and O on the surface allowing the reactants to collide and, with a transient close to a picosecond (ps), new electronic states appear in the O K-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond-formation between CO and O with a distribution of OC—O bond lengths close to the transition state (TS). After …
