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The diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes-Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle.

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Reference:
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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Since its inception a decade ago, sol-gel encapsulation has opened up an intriguing new way to immobilize biological materials. An array of substances, including catalytic antibodies, DNA, RNA, antigens, live bacterial, fungal, plant and animal cells, and whole protozoa, have been encapsulated in silica, metal-oxide, organosiloxane and hybrid sol-gel polymers. The advantages of these ‘living ceramics’ might give them applications as optical and electrochemical sensors, diagnostic devices, catalysts, and even bioartificial organs. With rapid advances in sol-gel precursors, nanoengineered polymers, encapsulation protocols and fabrication methods, this technology promises to revolutionize bioimmobilization. Copyright (C) 2000 Elsevier Science Ltd.

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Reference:
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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A kinetic study of the one electron oxidation of substituted ferrocenes (FcX: X = H, COPh, COMe, CO2Et, CONH2, CH2OH, Et, and Me2) by a series of N-oxyl radicals (succinimide-N-oxyl radical (SINO), maleimide-N-oxyl radical (MINO), 3-quinazolin-4-one-N-oxyl radical (QONO) and 3-benzotriazin-4-one-N-oxyl radical (BONO)), has been carried out in CH3CN. N-oxyl radicals were produced by hydrogen abstraction from the corresponding N-hydroxy derivatives by the cumyloxyl radical. With all systems, the rate constants exhibited a satisfactory fit to the Marcus equation allowing us to determine self-exchange reorganization energy values (lambdaNO/NO-) which have been compared with those previously determined for the PINO/PINO- and BTNO/BTNO- couples. Even small modification of the structure of the N-oxyl radicals lead to significant variation of the lambdaNO/NO- values. The lambdaNO/NO- values increase in the order BONO < BTNO < QONO < PINO < SINO < MINO which do not parallel the order of the oxidation potentials. The higher lambdaNO/NO- values found for the MINO and SINO radicals might be in accordance with a lower degree of spin delocalization in the radicals MINO and SINO and charge delocalization in the anions MINO- and SINO- due to the absence of an aromatic ring in their structure. This is the end of this tutorial post, and I hope it has helped your research about 1273-86-5, you can contact me at any time and look forward to more communication. SDS of cas: 1273-86-5

Reference:
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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Ferrocenylmethanol (Fc-OH) is included in beta-cyclodextrin (beta-CD) to form the beta-CD-Fc-OH complex by host-guest supramolecular interaction. beta-CD dissociates from the beta-CD-Fc-OH complex due to the conversion of Fc-OH to Fc+-OH under a stimulus of oxidant. In our study, Fc-OH is oxidized after a series of enzymatic reactions of creatinine, which blocks the other means for oxidation of Fc-OH. And the background noise is reduced for testing for serum creatinine (sCr). The chronoamperometry signal for creatinine (with a constant potential -0.3 V vs. Ag/AgCl) increases linearly in the 1 – 1000 muM range, with a limit of detection as low as 0.5 muM. The amperometric potential of -0.3 V greatly prevents the interference of various redox substances in serum. The biosensor was used to test 120 clinical specimens and the results showed a linear correlation with the biochemical analyzer (R2 = 0.9885). The biosensor could be applied to clinical trials and offers good prospects for clinical sCr detection.

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Reference:
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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Pyranose oxidase (POx) catalyzes the oxidation of D-glucose to 2-ketoglucose with concurrent reduction of oxygen to H2O2. POx from Trametes ochracea (ToPOx) is known to react with alternative electron acceptors including 1,4-benzoquinone (1,4-BQ), 2,6-dichlorophenol indophenol (DCPIP), and the ferrocenium ion. In this study, enzyme variants with improved electron acceptor turnover and reduced oxygen turnover were characterized as potential anode biocatalysts. Pre-steady-state kinetics of the oxidative half-reaction of ToPOx variants T166R, Q448H, L545C, and L547R with these alternative electron acceptors were evaluated using stopped-flow spectrophotometry. Higher kinetic constants were observed as compared to the wild-type ToPOx for some of the variants. Subsequently, the variants were immobilized on glassy carbon electrodes. Cyclic voltammetry measurements were performed to measure the electrochemical responses of these variants with glucose as substrate in the presence of 1,4-BQ, DCPIP, or ferrocene methanol as redox mediators. High catalytic efficiencies (Imax app/KM app) compared to the wild-type POx proved the potential of these variants for future bioelectrocatalytic applications, in biosensors or biofuel cells. Among the variants, L545C showed the most desirable properties as determined kinetically and electrochemically.

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Reference:
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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This paper describes an electrochemically mediated enzyme reaction of polyethyleneglycol (PEG)-modified galactose oxidase (GAO) in organic solvents as well as in an aqueous solution. Catalytic currents were investigated in the presence of ferrocene derivatives as mediators and PEG-modified GAO in several organic solvents. The catalytic current due to the mediated enzyme reaction was obtained in acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide (DMSO). Stability tests of PEG-modified GAO in organic solvents demonstrated that the initial Ik/Id value was highest in acetonitrile; however, it gradually decreased. The PEG-modified GAO was more stable in DMSO. Reactivities of several mediators were investigated. Although a positively charged mediator indicated high reactivity in the aqueous solution, non-charged mediators such as ferrocene dimethanol and n-butyl ferrocene showed the highest activity in organic solvents. Substrate specificity demonstrated that the catalytic activity for benzyl alcohol in acetonitrile was greater than in aqueous solution. The effect of water content in acetonitrile was investigated. The catalytic activity decreased with the increase in water content.

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Reference:
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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We present a non-invasive electrochemical strategy for mapping the antioxidant (AO) activity of apple peels, which counterbalances oxidative stress caused by various external effectors. Soft carbon microelectrodes were used for soft probe scanning electrochemical microscopy (SECM) enabling the gentle and scratch-free contact mode scanning of rough and delicate apple peels in an electrolyte solution. The SECM feedback mode was applied using ferrocene methanol (FcMeOH) as redox mediator that gets electrochemically oxidized at the soft probe and diffuses towards the apple peel where it gets regenerated by certain AOs leading to a redox mediator recycling and increased current signal. The global AO activity in the apple peel including lenticels and regions with artificially degraded AOs were mapped using the soft microelectrodes. Finally, in an apple cross-section the higher and homogeneous AO concentration in the peel with a heterogeneously decaying AO gradient towards the apple inward was visualized, demonstrating the adequate micrometer resolution of the SECM probe and the possibility to get information of the interior AO activity of the apple.

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Reference:
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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Glassy carbon (GC) electrode was modified with phenyl layer using electrochemical reduction of benzenediazonium tetrafluoroborate. The phenyl layer on GC inhibits direct electron transfer of ferrocyanide but allows for facile electrode kinetics of hydroxymethylferrocene (HMF) in solution-phase. Based on this selective electrochemical discrimination of phenyl layer, a voltammetric signal enhancement for the detection of HMF was studied at phenyl-modified GC electrode in phosphate buffer (pH = 7.2) solution containing ferrocyanide as a sacrificial species. The current amplification ratio (R) was found to be linear to the ferrocyanide concentration ranging from 0.1 to 10 mM.

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Reference:
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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The efficiency of the alkaloids quinine, cinchonine, cinchonidine and ephedrine, the aminoalcohols prolinol, and alaninol, as well as the aminoacids proline, and phenylalanine as catalysts for the enantioselective addition of diethylzinc to ferrocene carbaldehyde and benzaldehyde has been studied. The addition reactions proceeded with acceptable yields and low to moderate enantioselectivities. The side products ferrocenyl methanol and 1-ferrocenyl-1-propanone, observed during the additions to ferrocene carbaldehyde were isolated and characterized.

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Reference:
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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Molecular mobility has been traditionally invoked to explain physical and chemical stability of diverse pharmaceutical systems. Although the molecular mobility concept has been credited with creating a scientific basis for stabilization of amorphous pharmaceuticals and biopharmaceuticals, it has become increasingly clear that this approach represents only a partial description of the underlying fundamental principles. An additional mechanism is proposed herein to address 2 key questions: (1) the existence of unfrozen water (i.e., partial or complete freezing inhibition) in aqueous solutions at subzero temperatures and (2) the role of water in the chemical stability of amorphous pharmaceuticals. These apparently distant phenomena are linked via the concept of water clusters. In particular, freezing inhibition is associated with the confinement of water clusters in a solidified matrix of an amorphous solute, with nanoscaled water clusters being observed in aqueous glasses using wide-angle neutron scattering. The chemical instability is suggested to be directly related to the catalysis of proton transfer by water clusters, considering that proton transfer is the key elementary reaction in many chemical processes, including such common reactions as hydrolysis and deamidation.

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Reference:
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