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Covalent immobilization and SECM analysis in feedback mode of glucose oxidase on a modified oxidized silicon surface

Covalent immobilization of glucose oxidase (GOx) on oxidized silicon (SiO2) surfaces is detailed in view of producing interfaces with a simple, controlled and reproducible procedure that could be used in bioanalytical applications as those based on SECM detection. The procedure is based first on the formation of an amino-terminated propyl layer on a SiO2 substrate followed by addition and cross-linking of a polyoxyethylene bis(diglycidylether) and GOx mixture. The epoxide groups of the cross-linker react with amino groups allowing both the cross-linking with the enzyme (reaction with the free amino groups of the lysine residues) and the covalent attachment of the enzyme layer on the amino groups bound to the surface. SECM in feedback mode analysis provides a characterization of the modified surface and the measurement of the enzymatic activity depending on the concentrations of glucose and mediator. Kinetics analysis indicates that GOx maintains a large enzymatic activity and that the active enzymes remain reachable after their incorporation in the layer with the advantages of a robust immobilization.

Covalent immobilization and SECM analysis in feedback mode of glucose oxidase on a modified oxidized silicon surface

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Nano-impact electrochemistry: Analysis of single bioentities

A central challenge of sensor technology is that the sensitivity of analytical detection is required to reach a single analyte entity level, whether it is a molecule, a cell or a nanoparticle. The emergence of nano-impact electrochemistry (NIE) allows in situ detection of single analyte entity one at a time with simplicity, fast response and high throughput. NIE method was originally designed to characterize physical and chemical properties of the corresponding single nanoparticles, and has been later extended into the field of bio-analysis, enabling better understanding of biological heterogeneity and providing new route for developing new diagnostic devices for quantifying biological analytes. A wide range of biological species including DNA, RNA, enzymes, bacteria, vesicles and cells has been already studied using NIE method so far. In this review, we first summarize the basic principles of NIE for bio-analyte detection and then elaborate NIE based bio-analysis categorized by analyte types. Finally, we give an outlook on the future prospects of this field.

Nano-impact electrochemistry: Analysis of single bioentities

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Ferrocenylmethyl-functionalized 5-membered heterocycles: Synthesis, solid-state structure and electrochemical investigations

Treatment of Fe(eta5-C5H4CH2OH)2 (1) with two equivalents of ClC(O)R (2) (a, R = 2-cC4H3O; b, R = 2-cC4H3S; c, R = 2-cC4H3Se; d, R = 3-cC4H3S) produced the corresponding ferrocenylmethyl carboxylates Fe(eta5-C5H4CH2OC(O)R)2 (3a?d), while the reaction of FcCH2OLi (Fc = Fe(eta5-C5H5)(eta5-C5H4)) with 2,5-(ClC(O))2-cC4H2X (5) (a, X = O; b, X = S; c, X = Se) in a 2:1 molar ratio gave 2,5-(FcCH2OC(O))2-cC4H2X (6a?c). Compounds 3a?d and 6a?c were characterized by elemental analysis, NMR (1H and 13C{1H}) and IR spectroscopy. The molecular structures of 3a,b,d in the solid state were determined by single crystal X-ray structure analysis. Compound 3a crystallizes in the monoclinic space group P21/c, while 3b,d crystallize in the triclinic space group P-1¡¥. The ester groups and the heteroatoms are in an anti arrangement with respect to each other. Cyclic voltammetry measurements for 3a?d and 6a?c show reversible electrochemical processes (Fc/Fc+) between 165 and 176 mV for 3a?d, and 94 and 116 mV for 6a?cb, using [NnBu4][B(C6F5)4] as the supporting electrolyte. It was found that for 3a, a somewhat higher Fc/Fc+ redox potential (E0?) is observed when compared with the more electron-rich systems 3b,c,d. The molecular electronic structures of the title compounds were additionally investigated by DFT calculations, revealing different degrees of HOMO?LUMO energy gaps within the series, due to a lowering of the LUMO energy, depending on the nature of the heterocyclic ring.

Ferrocenylmethyl-functionalized 5-membered heterocycles: Synthesis, solid-state structure and electrochemical investigations

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Binding properties of ferrocene-glutathione conjugates as inhibitors and sensors for glutathione S-transferases

The binding properties of two electroactive glutathione-ferrocene conjugates that consist in glutathione attached to one or both of the cyclopentadienyl rings of ferrocene (GSFc and GSFcSG), to Schistosoma japonica glutathione S-transferase (SjGST) were studied by spectroscopy fluorescence, isothermal titration calorimetry (ITC) and differential pulse voltammetry (DPV). Such ferrocene conjugates resulted to be competitive inhibitors of glutathione S-transferase with an increased binding affinity relative to the natural substrate glutathione (GSH). We found that the conjugate having two glutathione units (GSFcSG) exhibits an affinity for SjGST approximately two orders of magnitude higher than GSH. Furthermore, it shows negative cooperativity with the affinity for the second binding site two orders of magnitude lower than that for the first one. We propose that the reason for such negative cooperativity is steric since, i) the obtained thermodynamic parameters do not indicate profound conformational changes upon GSFcSG binding and ii) docking studies have shown that, when bound, part of the first bound ligand invades the second site due to its large size. In addition, voltammetric measurements show a strong decrease of the peak current upon binding of ferrocene-glutathione conjugates to SjGST and provide very similar K values than those obtained by ITC. Moreover, the sensing ability, expressed by the sensitivity parameter shows that GSFcSG is much more sensitive than GSFc, for the detection of SjGST.

Binding properties of ferrocene-glutathione conjugates as inhibitors and sensors for glutathione S-transferases

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Light-controlled switching of the spin state of iron(III)

Controlled switching of the spin state of transition metal ions, particularly of FeII and FeIII, is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation with two different wavelengths reversibly switches its spin state between low-spin (S = 1/2) and high-spin (S = 5/2) in solution (DMSO-acetone, 2:598). The switching efficiency is 76% at room temperature. The system is neither oxygen nor water sensitive, and no fatigue was observed after more than 1000 switching cycles. Concomitant with the spin-flip is a change in redox potential by ~60 mV. Besides serving as a simple model for the first step of the cytochrome P450 catalytic cycle, the spin switch can be used to switch the spin-lattice relaxation time T1 of the water protons by a factor of 15.

Light-controlled switching of the spin state of iron(III)

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Products of hydrolysis of (ferrocenylmethyl)trimethylammonium iodide: Synthesis of hydroxymethylferrocene and bis(ferrocenylmethyl) ether

The attempted coupling of (ferrocenylmethyl)trimethylammonium iodide (1) with 1,4,7-(triformyl)-1,4,7,10-tetraazacyclododecane (2) in water led to the formation of the expected compound 1-(ferrocenemethyl)-4,7,10-(triformyl)-1,4,7,10-tetraazacyclododecane (3). In addition, hydrolysis of the ferrocenyl precursor 1 led to the formation of two other known compounds, hydroxymethylferrocene (4) and bis(ferrocenylmethyl) ether (5). An X-ray crystal structure determination of 4 revealed the presence of H-bonding between the hydroxyl groups of one molecule of 4 and the oxygen atom of an adjacent molecule resulting in a left-handed helical chain of molecules lying along the b-axis direction. The O?O distances are significantly shorter than those found in previously reported structures of hydroxymethylferrocene derivatives indicative of moderate strength H-bonding interactions. In the structure of 5, the orientation of the ferrocenyl groups are staggered relative to a vector comprising the two carbons of the C-O-C linker. Crown Copyright

Products of hydrolysis of (ferrocenylmethyl)trimethylammonium iodide: Synthesis of hydroxymethylferrocene and bis(ferrocenylmethyl) ether

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Phospholipase D as a catalyst: Application in phospholipid synthesis, molecular structure and protein engineering

Phospholipase D (Pld) Is A Useful Enzyme For Its Transphosphatidylation Activity, Which Enables The Enzymatic Synthesis Of Various Phospholipids (Pls). Many Reports Exist On Pld-Mediated Synthesis Of Natural And Tailor-Made Pls With Functional Head Groups, From Easily Available Lecithin Or Phosphatidylcholine. Early Studies On Pld-Mediated Synthesis Mainly Employed Enzymes Of Plant Origin, Which Were Later Supplanted By Ones From Microorganisms, Especially Actinomycetes. Many Plds Are Members Of The Pld Superfamily, Having One Or Two Copies Of A Signature Sequence, Hxkxxxxd Or Hkd Motif, In The Primary Structures. Pld Superfamily Members Share A Common Core Structure, And Thereby, A Common Catalytic Mechanism. The Catalysis Proceeds Via Two-Step Reaction With The Formation Of Phosphatidyl-Enzyme Intermediate. Both Of The Two Catalytic His Residues Are Critical In The Reaction Course, Where One Acts As A Nucleophile, While The Other Functions As A General Acid/Base. Pld Is Being Engineered To Improve Its Activity And Stability, Alter Head Group Specificity And Further Identify Catalytically Important Residues. Since The Knowledge On Pld Enzymology Is Constantly Expanding, This Review Focuses On Recent Advances In The Field, Regarding Pld-Catalyzed Synthesis Of Bioactive Pls, Deeper Understanding Of Substrate Recognition And Binding Mechanism, Altering Substrate Specificity, And Improving Thermostability. We Introduced Some Of Our Recent Results In Combination With Existing Facts To Further Deepen The Story On The Nature Of This Useful Enzyme.

Phospholipase D as a catalyst: Application in phospholipid synthesis, molecular structure and protein engineering

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Electrochemical restructuring of Gold electrodes with redox active species to create electrocatalytically active nanostructured surfaces

Electrochemical potential cycling of gold electrodes in commonly used redox active species to produce a nanostructured surface is introduced. A commercially available gold electrode when cycled in three redox active species including hexaammine ruthenium chloride, ferrocene methanol and ferricyanide shows rapid conversion of the surface into a nanostructured form within 50 cycles which usually requires hundreds of cycles in their absence. The active gold nanostructured electrode was characterized by cyclic voltammetry in acidic and alkaline electrolyte indicating the presence of different basal sites depending on the redox species employed. In addition, the active gold nanostructured surface shows higher electrocatalytic activity than the pristine polycrystalline gold electrode for glucose and ascorbic acid oxidation in alkaline media.

Electrochemical restructuring of Gold electrodes with redox active species to create electrocatalytically active nanostructured surfaces

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Electrospun gold nanofiber electrodes for biosensors

A new form of high surface area bioelectrode, based on nanofibers of electrospun gold with immobilized fructose dehydrogenase, was developed. The gold fibers were prepared by electroless deposition of gold nanoparticles on an electrospun poly(acrylonitrile)-HAuCl4 fiber. The material was characterized using electron microscopy, XRD and BET, as well as cyclic voltammetry and biochemical assay of the immobilized enzyme. The electrochemical surface area of the gold microfibers was 0.32¡À0.04m2/g. Fructose dehydrogenase was covalently coupled to the gold surface through glutaraldehyde crosslinks to a cystamine monolayer. The enzyme exhibited mediated electron transfer directly to the gold electrode and catalytic currents characteristic of fructose oxidation in the presence of a ferrocene methanol mediator were observed. The limit of detection of fructose was 11.7muM and the KM of the immobilized enzyme was 5mM. The microfiber electrode was stable over 20 cycles with a 3.05% standard deviation. The response time of the sensor was less than 2.2s and reached half maximum value within 3.6s. The sensor was proven to be accurate and precise in both serum and popular beverages sweetened with high fructose corn syrup. The addition of glucose isomerase enabled the sensor to perform with glucose, thus expanding the available analyte selection for the sensor.

Electrospun gold nanofiber electrodes for biosensors

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Matrix-assisted polymer pen lithography induced Staudinger Ligation

The Staudinger Ligation has been combined with Polymer Pen Lithography to create patterns of fluorescent and redox-active inks with 1-micrometer scale feature diameters over centimeter-scale areas. This report presents a straightforward strategy to expand the scope of organic reactions employed in surface science. The Royal Society of Chemistry 2012.

Matrix-assisted polymer pen lithography induced Staudinger Ligation

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Reference£º
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion