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Journal of Biological Inorganic... Mar 2020Oxygen affinity is an important property of metalloproteins that helps elucidate their reactivity profile and mechanism. Heretofore, oxygen affinity values were... (Review)
Review
Oxygen affinity is an important property of metalloproteins that helps elucidate their reactivity profile and mechanism. Heretofore, oxygen affinity values were determined either using flash photolysis and polarography techniques that require expensive instrumentation, or using oxygen titration methods which are erroneous at low nanomolar and at high millimolar oxygen concentrations. Here, we describe an inexpensive, easy-to-setup, and a one-pot method for oxygen affinity measurements that uses the enzyme chlorite dismutase (Cld) as a precise in situ oxygen source. Using this method, we measure thermodynamic and kinetic oxygen affinities (K and K) of different classes of heme and non-heme metalloproteins involved in oxygen transport, sensing, and catalysis. The method enables oxygen affinity measurements over a wide concentration range from 10 nM to 5 mM which is unattainable by simply diluting oxygen-saturated buffers. In turn, we were able to precisely measure oxygen affinities of a model set of eight different metalloproteins with affinities ranging from 48 ± 3 nM to 1.18 ± 0.03 mM. Overall, the Cld method is easy and inexpensive to set up, requires significantly lower quantities of protein, enables precise oxygen affinity measurements, and is applicable for proteins exhibiting nanomolar-to-millimolar affinity values.
Topics: Kinetics; Models, Molecular; Oxidoreductases; Oxygen; Thermodynamics
PubMed: 31897725
DOI: 10.1007/s00775-019-01750-6 -
Chemical Record (New York, N.Y.) Feb 2012For this special issue on 90 years of polarography, the following personal account describes how my early research in electrochemistry and polarography in the laboratory... (Review)
Review
For this special issue on 90 years of polarography, the following personal account describes how my early research in electrochemistry and polarography in the laboratory of Prof. Petr Zuman led to a major research effort in the determination of proteins for cancer detection and monitoring. It reviews the very recent history of nanoparticle labels and multiplexed detection in protein immunosensors. It then describes our journey of discovery that has led to ultrasensitive protein immunosensors achieved by combining nanostructured electrodes with particles labeled with up to ½ million enzymes that can detect down to as little as 1 fg mL(-1) protein in diluted serum. Our most mature multiple protein detection system is a microfluidic device with eight sensors coated with 5-nm gold nanoparticles that uses off-line protein detection with heavily labeled magnetic particles. This approach has led to reliable sub pg mL(-1) detection limits for multiple proteins, provides excellent correlation with referee ELISA methods, and is currently being used for validation of panels of biomarkers for oral and prostate cancer. The article ends with a section on future perspectives.
Topics: Biomarkers; Electrochemical Techniques; Humans; Immunoassay; Microfluidic Analytical Techniques; Nanoparticles; Proteins
PubMed: 22287094
DOI: 10.1002/tcr.201100034 -
Biosensors Nov 2019The benzodiazepine class of drugs are characterised by a readily electrochemically reducible azomethine group. A number are also substituted by other electrochemically... (Review)
Review
The benzodiazepine class of drugs are characterised by a readily electrochemically reducible azomethine group. A number are also substituted by other electrochemically active nitro, N-oxide, and carbonyl groups, making them readily accessible to electrochemical determination. Techniques such as polarography, voltammetry, and potentiometry have been employed for pharmaceutical and biomedical samples, requiring little sample preparation. This review describes current developments in the design and applications of electrochemical-based approaches for the determination of the benzodiazepine class of drugs form their introduction in the early 1960s to 2019. Throughout this period, state-of-the-art electroanalytical techniques have been reported for their determination. Polarography was first employed focused on mechanistic investigations. Subsequent studies showed the adsorption of many the benzodiazepines at Hg electrodes allowed for the highly sensitive technique of adsorptive stripping voltammetry to be employed. The development and introduction of other working electrode materials such as carbon led to techniques such as voltammetry to become commonly reported, and the modification of these electrodes has now become the most commonly employed approach using molecularly imprinting and nanotechnology.
Topics: Adsorption; Benzodiazepines; Biosensing Techniques; Electrochemical Techniques; Electrodes; Mercury; Molecular Structure; Surface Properties
PubMed: 31684040
DOI: 10.3390/bios9040130 -
Medicina (Kaunas, Lithuania) Mar 2022Background and Objectives: Due to the nutritional and behavioral patterns of children, their teeth can be a good indicator of heavy metal uptake from over the years. To...
Background and Objectives: Due to the nutritional and behavioral patterns of children, their teeth can be a good indicator of heavy metal uptake from over the years. To determine the amount of Zn, Cu, Cd, and Pb accumulated in the body, primary teeth of children in Zanjan, Iran, were examined with a polarography device. Materials and Methods: Samples were collected from dentistry clinics of Zanjan, Iran, and were prepared for acid digestion, and then were analyzed by a polarography device for determining the concentration of lead, copper, zinc, and cadmium. Results: Data were analyzed by a t-independent test to compare different groups (p < 0.05). Based on the results obtained from this study, the mean concentrations of zinc, lead, copper, and cadmium were 245, 7.66, 5.33, and 0.0879 µg/g, respectively, which shows that the amount of each of the four elements was more than the amounts that have been reported for different countries. The results showed no significant difference between age, tooth type, and jaw groups. Conclusions: We conclude that primary teeth are an important biological indicator to evaluate the concentration of heavy elements in the human body. The high concentrations of these elements in the primary teeth analyzed in this study could be attributed to the high concentrations of these elements in the environment of Zanjan.
Topics: Cadmium; Child; Dentistry; Humans; Metals, Heavy; Polarography; Zinc
PubMed: 35334624
DOI: 10.3390/medicina58030448 -
Nature Communications Dec 2019In the brain, increased neural activity is correlated with increases of cerebral blood flow and tissue oxygenation. However, how cerebral oxygen dynamics are controlled...
In the brain, increased neural activity is correlated with increases of cerebral blood flow and tissue oxygenation. However, how cerebral oxygen dynamics are controlled in the behaving animal remains unclear. We investigated to what extent cerebral oxygenation varies during locomotion. We measured oxygen levels in the cortex of awake, head-fixed mice during locomotion using polarography, spectroscopy, and two-photon phosphorescence lifetime measurements of oxygen sensors. We find that locomotion significantly and globally increases cerebral oxygenation, specifically in areas involved in locomotion, as well as in the frontal cortex and the olfactory bulb. The oxygenation increase persists when neural activity and functional hyperemia are blocked, occurred both in the tissue and in arteries feeding the brain, and is tightly correlated with respiration rate and the phase of respiration cycle. Thus, breathing rate is a key modulator of cerebral oxygenation and should be monitored during hemodynamic imaging, such as in BOLD fMRI.
Topics: Animals; Brain; Cerebrovascular Circulation; Female; Hemodynamics; Humans; Locomotion; Magnetic Resonance Imaging; Male; Mice, Inbred C57BL; Olfactory Bulb; Oxygen; Respiration; Wakefulness
PubMed: 31797933
DOI: 10.1038/s41467-019-13523-5 -
Materials (Basel, Switzerland) Dec 2023Tin determination allows for the monitoring of pollution and assessment of the impact of human activities on the environment. The determination of tin in the environment... (Review)
Review
Tin determination allows for the monitoring of pollution and assessment of the impact of human activities on the environment. The determination of tin in the environment is crucial for the protection of human health and ecosystems, and for maintaining sustainability. Tin can be released into the environment from various sources, such as industry, transportation, and electronic waste. The concentration of tin in the environment can be determined by different analytical methods, depending on the form of tin present and the purpose of the analysis. The choice of an appropriate method depends on the type of sample, concentration levels, and the available instrumentation. In this paper, we have carried out a literature review of electrochemical methods for the determination of tin. Electrochemical methods of analysis such as polarography, voltammetry, and potentiometry can be used for the determination of tin in various environmental samples, as well as in metal alloys. The detection limits and linearity ranges obtained for the determination of tin by different electrochemical techniques are collected and presented. The influence of the choice of base electrolyte and working electrode on signals is also presented. Practical applications of the developed tin determination methods in analyzing real samples are also summarized.
PubMed: 38138688
DOI: 10.3390/ma16247545 -
Archives of Emergency Medicine Sep 1989
Review
Topics: Hemodynamics; Humans; Monitoring, Physiologic; Muscles; Oxygen Consumption; Polarography; Shock
PubMed: 2675881
DOI: 10.1136/emj.6.3.172 -
Biochimica Et Biophysica Acta Apr 2004Photosystem II (PSII) produces dioxygen from water in a four-stepped process, which is driven by four quanta of light and catalysed by a Mn-cluster and tyrosine Z.... (Review)
Review
Photosystem II (PSII) produces dioxygen from water in a four-stepped process, which is driven by four quanta of light and catalysed by a Mn-cluster and tyrosine Z. Oxygen is liberated during one step, coined S(3)=>S(0). Chemical intermediates on the way from reversibly bound water to dioxygen have not yet been tracked, however, a break in the Arrhenius plot of the oxygen-evolving step has been taken as evidence for its existence. We scrutinised the temperature dependence of (i) UV-absorption transients attributable to the reduction of the Mn-cluster and tyrosine Z by water, and (ii) polarographic transients attributable to the release of dioxygen. Using a centrifugatable and kinetically competent Pt-electrode, we observed no deviation from a linear Arrhenius plot of oxygen release in the temperature range from -2 to 32 degrees C, and hence no evidence, by this approach, for a sufficiently long-lived chemical intermediate. The half-rise times of oxygen release differed between Synechocystis WT* (at 20 degrees C: 1.35 ms) and a point mutant (D1-D61N: 13.1 ms), and the activation energies differed between species (Spinacia oleracea, 30 kJ/mol versus Synechocystis, 41 kJ/mol) and preparations (PSII membranes, 41 kJ/mol versus core complexes, 33 kJ/mol, Synechocystis). Correction for polarographic artefacts revealed, for the first time, a temperature-dependent lag-phase of the polarographic transient (duration at 20 degrees C: 0.45 ms, activation energy: 31 kJ/mol), which was indicative of a short-lived intermediate. It was, however, not apparent in the UV-transients. Thus the "intermediate" was probably newly formed and transiently bound oxygen.
Topics: Cyanobacteria; Electron Transport; Kinetics; Manganese; Mutation; Oxidation-Reduction; Oxygen; Photosystem II Protein Complex; Polarography; Spectrophotometry, Ultraviolet; Temperature; Thermodynamics
PubMed: 15100031
DOI: 10.1016/j.bbabio.2003.06.001 -
Cerebral Cortex (New York, N.Y. : 1991) Jan 2016The human default mode network (DMN) shows decreased blood oxygen level dependent (BOLD) signals in response to a wide range of attention-demanding tasks. Our...
The human default mode network (DMN) shows decreased blood oxygen level dependent (BOLD) signals in response to a wide range of attention-demanding tasks. Our understanding of the specifics regarding the neural activity underlying these "task-negative" BOLD responses remains incomplete. We paired oxygen polarography, an electrode-based oxygen measurement technique, with standard electrophysiological recording to assess the relationship of oxygen and neural activity in task-negative posterior cingulate cortex (PCC), a hub of the DMN, and visually responsive task-positive area V3 in the awake macaque. In response to engaging visual stimulation, oxygen, LFP power, and multi-unit activity in PCC showed transient activation followed by sustained suppression. In V3, oxygen, LFP power, and multi-unit activity showed an initial phasic response to the stimulus followed by sustained activation. Oxygen responses were correlated with LFP power in both areas, although the apparent hemodynamic coupling between oxygen level and electrophysiology differed across areas. Our results suggest that oxygen responses reflect changes in LFP power and multi-unit activity and that either the coupling of neural activity to blood flow and metabolism differs between PCC and V3 or computing a linear transformation from a single LFP band to oxygen level does not capture the true physiological process.
Topics: Action Potentials; Animals; Attention; Brain Mapping; Evoked Potentials, Visual; Image Processing, Computer-Assisted; Macaca; Magnetic Resonance Imaging; Neurons; Oxygen; Photic Stimulation; Visual Cortex; Visual Perception
PubMed: 25385710
DOI: 10.1093/cercor/bhu260