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The effect of cathodic polarization on the electrochemical behavior of the thin titanium dioxide film formed by anodic pretreatment over pure commercial titanium metal for biomaterial application was investigated in situ using scanning electrochemical microscopy (SECM). Quantitative information on the electron transfer rates (keff) at the titanium surface was obtained using the feedback operation of SECM with ferrocene-methanol (FcMeOH) as electrochemical mediator. An increase of keff values with the increase of the negative polarization was detected, a feature that correlates well with the decrease of titanium oxide resistance with increasing cathodic polarization observed using electrochemical impedance spectroscopy (EIS). In addition, SECM operation in the redox competition mode proved that hydrogen was absorbed in the surface oxide film leading to changes in conductivity and electrochemical reactivity.

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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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An electrochemical Lab-on-a-Disc (eLoaD) platform for the automated quantification of ovarian cancer cells (SKOV3) from whole blood is reported. This centrifugal microfluidic system combines complex sample handling, i.e., blood separation and cancer cell extraction from plasma, with specific capture and sensitive detection using label-free electrochemical impedance. Flow control is facilitated using rotationally actuated valving strategies including siphoning, capillary and centrifugo-pneumatic dissolvable-film (DF) valves. For the detection systems, the thiol-containing amino acid, l-Cysteine, was self-assembled onto smooth gold electrodes and functionalized with anti-EpCAM. By adjusting the concentration of buffer electrolyte, the thickness of the electrical double layer was extended so the interfacial electric field interacts with the bound cells. Significant impedance changes were recorded at 117.2Hz and 46.5Hz upon cell capture. Applying AC amplitude of 50mV at 117.2Hz and open circuit potential, a minimum of 214capturedcells/mm2 and 87% capture efficiency could be recorded. The eLoaD platform can perform five different assays in parallel with linear dynamic range between 16,400 and (2.6±0.0003)×106cancercells/mL of blood, i.e. covering nearly three orders of magnitude. Using the electrode area of 15.3mm2 and an SKOV3 cell radius of 5mum, the lower detection limit is equivalent to a fractional surface coverage of approximately 2%, thus making eLoaD a highly sensitive and efficient prognostic tool that can be developed for clinical settings where ease of handling and minimal sample preparation are paramount.

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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 ever-increasing demands for clean and sustainable energy sources combined with rapid advances in biointegrated portable or implantable electronic devices have stimulated intensive research activities in enzymatic (bio)fuel cells (EFCs). The use of renewable biocatalysts, the utilization of abundant green, safe, and high energy density fuels, together with the capability of working at modest and biocompatible conditions make EFCs promising as next generation alternative power sources. However, the main challenges (low energy density, relatively low power density, poor operational stability, and limited voltage output) hinder future applications of EFCs. This review aims at exploring the underlying mechanism of EFCs and providing possible practical strategies, methodologies and insights to tackle these issues. First, this review summarizes approaches in achieving high energy densities in EFCs, particularly, employing enzyme cascades for the deep/complete oxidation of fuels. Second, strategies for increasing power densities in EFCs, including increasing enzyme activities, facilitating electron transfers, employing nanomaterials, and designing more efficient enzyme-electrode interfaces, are described. The potential of EFCs/(super)capacitor combination is discussed. Third, the review evaluates a range of strategies for improving the stability of EFCs, including the use of different enzyme immobilization approaches, tuning enzyme properties, designing protective matrixes, and using microbial surface displaying enzymes. Fourth, approaches for the improvement of the cell voltage of EFCs are highlighted. Finally, future developments and a prospective on EFCs are envisioned.

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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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The stability of thin silicate films in solution has been evaluated as a function of drying time and drying conditions using scanning probe microscopy and an electrochemical probe technique. In these experiments, the silicate films were spin coated on various substrates using a sol formed by the acid catalyzed hydrolysis and condensation of tetramethoxysilane. The silicate films were then dried under a relative humidity of 25, 50, or 75% for 3, 12, 24, or 48 h. After drying, the films were immediately placed in a solution of potassium nitrate or a solution of a redox probe, specifically ferrocene methanol, ruthenium hexaammine, or cobalt phenanthroline. Cyclic voltammetry in conjunction with atomic force microscopy was used to monitor the disruption in gel structure as the films sat in aqueous solution. The stability of each film was found to be essentially independent of the substrate it was coated on but a strong function of the length of the drying time and the relative humidity under which it was dried. Films that were dried at 25% humidity for 48 h stayed on the electrode for several days. In contrast, films that were dried at 75% humidity for 3 h fell off the electrode within 24 h.

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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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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 report the synthesis, characterization, and cytotoxic and antimalarial activity of ferrocene-indole hybrids 8-14. The 2-phenylindole scaffold was chosen because of its potent antimitotic activity and ferrocene was chosen following the development of ferrocifens, ferrocene derivatives of tamoxifen, which are prototypes of a new family of organometallic anti-estrogens. Ferrocene-indole hybrids 8-14 and their corresponding organic analogues 1-7 showed only moderate antimalarial activities, while ferrocene-indole hybrids 11 and 12 showed excellent in vitro activities against the A549 human carcinoma cell line, with IC50 values of 5 and 7 muM respectively. These ferrocene-indole hybrids were up to 25-fold more potent as cytotoxic agents than their purely organic analogues.

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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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A glucose-modified dendritic hydrogel is used as a bioink for bacterial encapsulation. This biocompatible hydrogel is a potentially suitable alternative to conventional alginate hydrogel for bacterial encapsulation, as it readily forms gel in the presence of Na+ or K+ ions without any additional stimuli such as pH, temperature, sonication, or the presence of divalent metal ions. We created a bacterial microhabitat by adding the gelator to phosphate-buffered saline containing live bacteria at physiological pH and using an additive three-dimensional (3D) printing technique. The bacteria remained viable and metabolically active within the 3D printed bacterial microhabitat, as shown with confocal laser scanning microscopy and scanning electrochemical microscopy.

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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 communication reports a new nanocatalytic scheme based on the facts that the redox reaction between a highly outer-sphere-reaction-philic (OSR-philic) species and a highly inner-sphere-reaction-philic (ISR-philic) species is slow and that an OSR- and ISR-philic Au-nanocatalyst label can mediate the two different types of redox species. This scheme allows highly sensitive and incubation free detection of creatine kinase-MB.

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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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57Fe NMR-spectra of 28 mono and disubstituted ferrocenes with a natural abundance of 57Fe have been measured relative to internal ferrocene.Most of the resonances appear at the high frequency side.The shielding influence of the various substituents is discussed qualitatively. 57Fe shifts are very sensitive to ring tilting as occurring in <3>ferrocenophanes. – Keywords: 57Fe Shifts; Hybridization influence on chemical shifts; Ring tilting

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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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alpha-Ferrocenylalkyl carbonates were demonstrated to be the species for ferrocenylalkylation reactions. The alpha-ferrocenylalkyl carbonates FcCH(R)OCOOEt (1a-c, Fc = ferrocenyl) were easily generated in situ by a reaction of the alpha-ferrocenyl substituted alcohols FcCH(R)OH (5a-c) with equimolar amounts of n-BuLi followed by EtOCOCl in THF or Et2O at 20 C. Due to the low thermal stability, carbonates 1a-c readily undergo a heterolytical decay furnishing the alpha-ferrocenyl carbocations FcCH(R)+ (2a-c) and carbonate anion R’OC(O)O? (3). The last one reversibly loses a molecule of CO2 giving rise anion EtO? that is capable of deprotonating a pre-nucleophile NuH (MeCOCH2COMe, dimethyl malonate, etc.) giving rise the corresponding nucleophile Nu?. The interaction between 2a-c and Nu? produces the alpha-ferrocenylalkylation products FcCH(R)Nu (4a-c) in moderate to high yields. The sequence above is a novel alpha-ferrocenylalkylation procedure easily proceeding under mild and neutral conditions. Due to these features, it may be useful for alpha-ferrocenylalkylations of either thermally labile compounds or the substrates susceptible to acidic conditions. The stability of carbonates 1a-c was found to decrease as the stability of the corresponding carbocations 2a-c increases. With 2-mercapto-1-methylimidazole, the alpha-ferrocenylalkylations proceed as the N-alkylation processes.

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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