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This review summarizes the basic features of the PQQ-GDH enzyme as one of the sugar converting biocatalysts. Focus is on the membrane -bound and the soluble form. Furthermore, the main principles of enzymatic catalysis as well as studies on the physiological importance are reviewed. A short overview is given on developments in protein engineering. The major part, however, deals with the different fields of application in bioelectrochemistry. This includes approaches for enzyme-electrode communication such as direct electron transfer, mediator-based systems, redox polymers or conducting polymers and holoenzyme reconstitution, and covers applied areas such as biosensing, biofuel cells, recycling schemes, enzyme competition, light-directed sensing, switchable detection schemes, logical operations by enzyme electrodes and immune sensing.

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Acylferrocenes reacted with samarium diiodide in the presence of water to give the corresponding (alpha-hydroxyalkyl)ferrocenes or alkylferrocenes depending on the reaction time and temperature. On treatment with samarium diiodide in the absence of water, ferrocenecarbaldehyde underwent a reductive coupling to give pinacols, whereas acetylferrocene yielded 3,3-diferrocenyl-2-butanone and 2,3-diferrocenyl-2-butene via the subsequent rearrangement and deoxygenation.

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The easy vinyl sulfone derivatization of ferrocene allows the preparation of some effective, versatile and valuable ferrocenylation reagents. The applicability of such compounds in conjugation and bioconjugation of amine and/or thiol containing molecules and biomolecules through Michael-type addition under mild conditions that preserve the biological function of the latter is described. The feasibility of the methodology is demonstrated by the preparation of a variety of conjugates and bioconjugates (ferrocenyl terminated dendrimers and ferrocene-sugar, ferrocene-cyclodextrin, ferrocene-peptide and ferrocene-protein conjugates).

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Further advances in understanding the mechanism of action of resveratrol and its application require new analogs to identify the structural determinants for the cell proliferation inhibition potency. Therefore, we synthesized new trans-resveratrol derivatives by using the Wittig and Heck methods, thus modifying the hydroxylation and methoxylation patterns of the parent molecule. Moreover, we also synthesized new ferrocenylstilbene analogs by using an original protective group in the Wittig procedure. By performing cell proliferation assays we observed that the resveratrol derivatives show inhibition on the human colorectal tumor SW480 cell line. On the other hand, cell viability/cytotoxicity assays showed a weaker effects on the human hepatoblastoma HepG2 cell line. Importantly, the lack of effect on non-tumor cells (IEC18 intestinal epithelium cells) demonstrates the selectivity of these molecules for cancer cells. Here, we show that the numbers and positions of hydroxy and methoxy groups are crucial for the inhibition efficacy. In addition, the presence of at least one phenolic group is essential for the antitumoral activity. Moreover, in the series of ferrocenylstilbene analogs, the presence of a hidden phenolic function allows for a better solubilization in the cellular environment and significantly increases the antitumoral activity.

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Pd(OAc)2-catalyzed Sonogashira coupling reactions of alkynes and a variety of aryl halides with 1,3-bis(5-ferrocenylisoxazoline-3-yl)benzene as an efficient non-phosphorus ligand under copper-free conditions are presented. The main advantages over previous methodologies include low catalyst loading (0.2 mol% Pd(OAc)2 and 0.4 mol% ferrocenyl bisoxazoline ligand are sufficient for these coupling reactions), less problematic reaction medium (water?dimethylformamide) and more convenient operation (no requirement for nitrogen protection).

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The diiron bridging vinyliminium complexes [Fe2{mu- eta1:eta3-C=N(Me)2C(R?)=C(R?)} (mu-CO)(CO)(Cp)2][SO3CF3] (R? = H, R? = SiMe3, 3a; R? = H, R? = Tol =4-MeC 6H4, 3b; R? = Me, R? = Me, 3c; R? = SPh, R? = Me, 3d; R? = H, R? = Fc = [Fe(C5H 4)(Cp)], 6e) react with propargyl alcohol (HC?CCH 2OH), in refluxing toluene, affording the polysubstituted ferrocenes as mixtures of two isomeric forms: [1-NMe2-2-R?-3-R?-5- CH2OCH2C?CH-Fc] (R? = H, R? = SiMe 3, 6a; R? = H, R? = Tol, 6b; R? = Me, R? = Me, 6c; R? = SPh, R? = Me, 6d, R? = H, R? = Fc, 6e) and [1-NMe2-2-R?-3-R?-4-CH2OCH2C? CH-Fc] (R? = H, R? = SiMe3, 7a; R? = H, R? = Tol, 7b; R? = Me, R? = Me, 7c; R? = SPh, R? = Me, 7d) in overall yields of about 55-65%. Formation of the functionalized cyclopentadienyl in the ferrocene products takes place through the assembly of two propargyl units with the bridging vinyliminium ligand: one alkynol is incorporated by a [3 + 2] cycloaddition with the bridging C3 ligand; a second alkynol unit gives rise to a pendant chain through -OH substitution. Investigations show that the substitution step is catalyzed by the parent diiron complex itself or by a mononuclear iron fragment (likely the Fp+ complex). The pendant propargyl chain has been exploited to connect the ferrocene to other molecular fragments: in particular, the reaction of 6a with 4-biphenyl azide, by copper-catalyzed azide-alkyne cycloaddition (CuAAC), leads to the formation of the triazole-functionalized ferrocene [1-NMe 2-2-CH2OCH2-N3(C6H 4Ph)C2H-4-SiMe3-Fc] (12). Moreover, 6a reacts with Co2(CO)8, affording the complex [Co 2{mu-eta2-HC?CR}(CO)6] (13), (HC?CR = 6a), where the alkyne adopts a eta2 coordination to a dicobalt hexacarbonyl fragment. The molecular structure of 7a has been determined by X-ray diffraction studies.

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In the present work we develop a real-time electrochemical mediator assay to enable the assessment of cell numbers and chemical toxicity. This allowed us to monitor metabolism down to a single cell in a low cost easy to use rapid assay which is not possible with current technology. The developed assay was based on the determination of oxygen. This was made possible via the use of electrochemical mediator ferrocene carboxylic acid (FcA). The FcA showed distinctive catalytic properties in interacting with reactive oxygen species generated from oxygen when compared to ferrocene methanol (FcMeOH). A deeper insight into the chemistry controlling this behaviour is provided. The behaviour is then taken advantage of to develop a cellular aerobic respiration assay. We describe the properties of the FcA system to detect, in real-time, the oxygen consumption of Escherichia coli DH5-alpha (E. coli). We demonstrated that the FcA-based oxygen assay is highly sensitive, and using a population of cells, oxygen consumption rates could be calculated down to a single cell level. More importantly, the results can be accomplished in minutes, considerably outperforming current commercially available biooxygen demand assays. The developed assay is expected to have a significant impact in diverse fields and industries, ranging from environmental toxicology through to pharmaceutical and agrochemical industries.

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This paper describes the orbital configuration which provides a basis for the understanding of the electronic structure and spectroscopic properties of 17e and 18e FcC2R and FcC4R dyads, where R is H, 1-naphthyl, 9-anthryl, 3-pyrenyl, perylenyl. DFT calculations show that destabilisation of the ferrocenyl pi orbitals upon binding a C{triple bond, long}CR group to a Cp ring leads to the metal-based a1 orbital dropping below the e1-a so that the frontier orbital configuration is (e2? -a, pi)2 (e2? -b,metal)2 (e1? -a, pi)2, (a1, metal)2. The contribution of the aryl group to the pi e2-a and e1-a orbitals varies with the annelation of the ring. The LUMO is aryl based. The calculations are consistent with the spectroscopic data for the 18e species. Oxidation to the 17e cations does not change the orbital configuration but the orbital energies are lowered by the positive charge centred on the Fe. A strongly solvatochromic transition in the near-IR, a signature for the 17e cations, is best described as an LMCT transition but the contribution of C2R and C4R to the donor and acceptor levels depends on the ionization energy of the aryl pi orbital. LMCT energies decrease from FcC2R to FcC4R dyads.

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Highly effective asymmetric hydrogenation of various ferrocenyl ketones, including aliphatic ferrocenyl ketones as well as the more challenging aryl ferrocenyl ketones, was realized in the presence of a Ru/diphosphine/diamine bifunctional catalytic system. Excellent enantioselectivities (up to 99.8% ee) and activities (S/C = 5000) could be obtained. These asymmetric hydrogenations provided a convenient and efficient synthetic method for chiral ferrocenyl alcohols, which are key intermediates for a variety of chiral ferrocenyl ligands and resolving reagents.

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Since oxidation and reduction reactions mainly take place on surfaces, enlarging the specific surface of redox materials is the key to achieving excellent electrochemical performance. In this work, by using silica monolayer colloidal crystal templates (MCCTs), a nanostructured Fc(COCH3)2 film is prepared successfully, and such a nanostructure could exhibit the following unique electrochemical properties: the MCCTs could impede the aggregation tendency of Fc(COCH3)2 and possess high electrochemical activity; Fc(COCH3)2 enlarges the contact area and offers more active sites and faster electronic transmission channels. The structure, optical and electrochemical properties of the nanostructured Fc(COCH3)2 were tested and then compared with those of compact Fc(COCH3)2 films to evaluate the role of the nanoarchitecture. The unique structure design of the Fc(COCH3)2 film enables outstanding performance, showing a large transmittance change (DeltaT) of 37% at 550 nm when switched between 0.5 V and -2.5 V, which is approximately ninefold higher than that of the compact Fc(COCH3)2 film (approximately 4%). Response times of coloration and bleaching are found to be only 16.15 s and 5.56 s. Furthermore, the nanostructured Fc(COCH3)2 film shows much better cycling stability than the compact one. The results indicate that the nanostructure could significantly improve the electrochemical performance of the Fc(COCH3)2 film due to the increase in electrochemical active sites and the enhancement of the “D-to-A” redox switch of ferrocene.

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