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Electrochemistry of Phospholes
Koláčná, Lucie ; Liška, Alan ; Ludvík, Jiří
Seventeen pentasubstituted phospholes with expected application in organic electronics were\nsynthesized and characterized electrochemically and by UV-vis spectra. Quantum chemical\ncalculations ofredox potentials and HOMO-LUMO energies were performed and experimental\nand theoretical data were successfully correlated. Tuning of redox properties can be achieved\nby combination of induction and resonance effects of substituents, extension / diminution of\nthe pi- delocalized system and by steric changes which affect intramolecular electron\ncommunication.
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Voltametrické stanovení těžkých kovů ve včelím jedu za použití rtuťové kapkové elektrody a uhlíkového vodivého filamentu pro 3D tisk
Navrátil, Tomáš ; Choińska-Mlynarczyk, Marta ; Šestáková, Ivana ; Hrdlička, Vojtěch
Včelí jed představuje sekret z jedového ústrojí včelích dělnic nebo včelí matky (nikoliv trubců).\nSmrtelná dávka pro člověka je asi 400-700 žihadel, LD50 myší i.v.=0,6 mg/kg. Po vysušení\nvzniká světle žlutý, velmi jemný prášek. Je rozpustný ve vodě za vzniku opaleskujícího roztoku.\nTypické složení (procenta představují podíl látky v sušině):\n -50-55 % silně bazický polypeptid melitin (poškozuje červené i bílé krvinky), 2-3 %\nappamin (vliv na nervovou soustavu), MCD (mast cell degranulating) peptid (narušuje\nčinnost buněčných membrán,\n Enzymy: 13-14 % fosfolypáza A a B, 2-3 % hyaluronidáza,\n Biogenní aminy: histamin, dopamin, noradrenalin.\nKromě výše uvedených látek jsou v jedu, podobně jako ve včelím medu, obsaženy látky, se\nkterými přichází tento blanokřídlý hmyz do styku během svého života. Jedná se tedy i o těžké\nkovy, kterými je kontaminováno naše životní prostředí. Analýza včelího jedu včel\nmedonosných žijících ve zvolené oblasti může tedy poskytnout informaci o plošném znečištění\npoměrně velké oblasti.
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Metalothioneiny jako biomarkery znečištění životního prostředí
Šestáková, Ivana ; Křivská, D. ; Navrátil, Tomáš
Sledování obsahu metalothioneinů jako biomarkeru znečištění vodního prostředí je\npředmětem řady studií i mezinárodního programu (Mediterranean Action Plan of The United\nNations Environment Program, 1999). Pro sledování vlivu kontaminace půdy jsou vhodnou\nmožností volně žijící drobní savci, kde hladiny metalothioneinů závisí na obsazích kovů\nv půdě, a i na dietních zvyklostech (omnivoři, herbivoři, karnivoři). V posledním desetiletí\nnabývají na významu studie vlivu parazitů, kde je popisován jak pozitivní, tak negativní vliv\nparazitů na obsahy kovů ve tkáních hostitele. U některých parazitů ryb byl zjištěn řádový nárůst\nobsahu kovů ve tkáních parazitu, který vedl k uvažování možnosti užití právě parazitů jako\nindikátoru znečištění.
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Determination of Selected Drugs using 3D Printed Electrodes
Choińska-Mlynarczyk, Marta ; Hrdlička, Vojtěch ; Navrátil, Tomáš
The main aim of this research was to develop a new method for voltammetric determination of\npopular antidepressants, analgesics, and illicit drugs using a laboratory-made 3D printed\nelectrode and to compare the achieved results with those registered using a commercially\navailable glassy carbon electrode. These experiments represent the first step in the development\nof a method applicable in clinical and forensic praxis for the rapid and inexpensive\ndetermination of commonly misused groups of biologically active compounds.
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The use of Boron Doped Diamond Electrode for Determination of 5-hydroxyindoleacetic Acid
Hrdlička, Vojtěch ; Navrátil, Tomáš
A new method for voltammetric determination of clinical biomarker 5-hydroxyindoleacetic\nacid (HIAA) at the boron-doped diamond electrode (BDDE) was developed. Anodically and\ncathodically pretreated BDDEs were tested in the pH ranges from 1 to 12, pre-treatment at\n+2.0V/60 s, and pH 3 was found to be the optimum.\nThe optimum square wave voltammetry (SWV) parameters were: f = 12 Hz, amplitude 60\nmV, and potential step 4 mV. SWV concentration dependency was constructed in the range\nfrom 0.1 to 100 μmol L−1, limits of determination and detection were 0.3 and 0.1 μmol L−1,\nrespectively. HIAA oxidation electrode process at BDDE was diffusion-controlled, as\nuncovered by cyclic voltammetry. Interestingly, HIAA peak potential was constant in various\nranges of pH, indicating a non-Nernstian behavior at the BDDE, in contrast to a previously\npublished electrooxidation mechanism consisting of a coupled H+/e− transfer.
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Ion Transfer Voltammetry across the Polarized Ionic Liquid/Water Interface: Base for Electrochemical Sensors
Langmaier, Jan ; Samec, Zdeněk
Some electrochemical techniques such as voltammetry at the polarized interfaces between two\nimmiscible electrolyte solutions (ITIES) represent interesting alternatives to classical\nelectrochemistry. The benefit of the ion transfer voltammetry lies in the possibility of detection\nof ionic species which are not otherwise redox active. The methodology enables apart of direct\ndetermination of ionic samples (including pharmaceutical and clinical ones) also to monitor\nreaction processes (acido-basic, enzymatic, etc.), determination of reaction substrates and\nproducts in one experimental step, evaluation of reaction and transport kinetics, and estimation\nof lipophilicity of involved species.
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Preparation, Testing and Application of Amalgam Screen-Printed Electrodes
Josypčuk, Bohdan ; Langmaier, Jan ; Tvorynska, Sofiia
Silver amalgam screen-printed electrodes (AgA-SPEs) were designed, prepared, and tested for\nthe first time as perspective representatives among SPEs for measuring at high negative\npotentials. The precise coulometric preparation procedure for mercury deposition at the\nworking electrode surface of the commercial silver-SPE was developed. An optimal\nelectrolyzer construction for the mercury deposition, electrolyte composition, and electrolysis\nconditions were proposed. The maximum value of hydrogen overvoltage (-1979 ± 4 mV) was\nfound on AgA-SPE with 50% (w/w) of Hg content in 0.1 mol L-1 NaOH, which is more negative\nthan with the original silver-SPE for 387 mV (-1592 ± 12 mV).
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Comparison of the Covalent Laccase Immobilization at Amino- and Carboxylfunctionalized Mesoporous Silica, Glassy Carbon, and Graphite Powders using Different Coupling Agents for Optimal Biosensor Preparation
Tvorynska, Sofiia ; Barek, J. ; Josypčuk, Bohdan
In order to find the most suitable immobilization protocol, a comparison of three strategies\nbased on the application of –NH2 and –COOH functionalized supports with the different\nactivation agents (glutaraldehyde and carbodiimide) have been conducted for the covalent\nenzyme (laccase) attachment. Two kinds of the supports, namely mesoporous silica (SBA−15,\nMCM−41) and carbonaceous (glassy carbon, graphite) powders, have been used. It was found\nthat a biosensor consisted of tubular detector of silver solid amalgam as a working electrode\nand the enzymatic mini-reactor with laccase covalently attached to glutaraldehyde activated\n–NH2 functionalized MCM−41 shows the best results regarding sensitivity and stability for\ndopamine detection.
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Construction and application of the amperometric uric acid biosensors based on the covalent immobilization of uricase by different strategies
Tvorynska, Sofiia ; Barek, J. ; Josypčuk, Bohdan
In this work, a promising combination of a biosensor based on the\nenzymatic mini-reactor with the detection principle of four-electron\nreduction of the consumed oxygen at highly negative potential has\nbeen developed for uric acid determination using flow injection\nanalysis. The construction of the biosensor provides a spatial\nsegregation of the biorecognition (uricase-based mini-reactor) and\ndetection (tubular detector of silver solid amalgam (TD-p-AgSA))\nparts. To find out the most appropriate enzyme immobilization\nprotocol, three different strategies of the covalent attachment for\nuricase from Bacillus fastidiosus have been compared. It was found\nthat the biosensor with the mini-reactor based on the covalent\nattachment of uricase via glutaraldehyde to -NH2 functionalized\nmesoporous silica powder MCM-41 showed extremely high stability\n(>1 year) and reusability (at least 600 measurements) The biosensor's\npractical applicability was confirmed by successful determination\nof uric acid in human urine.
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3D printed materials for the electrochemical determination of biologically active compounds
Choińska, Marta Katarzyna ; Navrátil, Tomáš ; Hrdlička, Vojtěch
3D printing materials are relatively novel materials in electrochemistry,\nused for manufacturing of electrochemical cells, electrodes\netc. They have been widely used mainly for tailored, fast, inexpensive,\nand easy preparation of various equipment for analyses of\nbiologically active compounds. Various medicinal products and illicit\ndrugs belong to this broad group of analytes which need to be\nmonitored because of the possibility of (un)intentional overdose or\nrecreational consumption, which can cause serious side effects or\neven death. Due to this risk, we decided to focus our research on the\ndevelopment of new, sensitive, selective, and easily customizable 3D\nprinted sensors for the determination of some commonly used\nantidepressants, analgesics, and illicit drugs.
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