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Phosphorene is a two-dimensional material that has many advantageous electronic, electrochemical, and optical properties. However, phosphorene possesses a relatively poor stability in ambient atmosphere. This disadvantage limits its application in several systems and particularly in electrochemical biosensors. Here we evaluate phosphorene as an electrochemical biosensing platform in two different mediator-based oxidoreductase enzymatic systems (glucose oxidase (GOx) and peroxidase from horseradish (HRP)), in which their detection is based on the reduction or oxidation of a mediator. In both cases, the used mediator is the same, ferrocene methanol (FcMeOH). Enhanced electrochemical activity is observed only in the reductive system (HRP-based biosensor) when compared to the oxidative counterpart (GOx-based biosensor). This phenomenon is attributed to the fact that in a reductive environment the phosphorene structure remains intact, while in an oxidative potential, the phosphorene is readily oxidized. In this way, the electroactivity of phosphorene as a sensing platform is strongly dependent on the type of mediator-based enzymatic system. These findings of binary nature of phosphorene are of high importance for construction of phosphorene-sensing platforms and in the development of enzyme logic systems.

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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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Malignant melanoma is a highly lethal disease, and advanced stages of melanoma have proven to be resistant to many chemotherapeutic drugs. Cancer stem cells (CSCs) and high levels of intracellular glutathione (GSH) have been proven to play important roles in drug resistance. Retinoic acid (RA) is a promising anticancer agent, which can inhibit proliferation and induce differentiation of CSCs, but its clinical use has been limited by its water insolubility and weak cancer cell killing effect when used alone. Herein, by combining RA and ferrocene, a new type of derivative of retinoic acid (FCRA) was synthesized and then oxidized by FeCl3. The oxidized FCRA (FCRA+) was exploited as a novel anticancer agent. Compared with RA, FCRA+ not only has improved water solubility and stronger anti-cancer effect to melanoma cells through depleting intracellular GSH of the cancer cells, but also can inhibit proliferation and induce differentiation of melanoma CSCs, such as free RA. Therefore, FCRA+ has better application prospects than RA and may replace RA for clinical applications.

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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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Voltage responsive micelles prepared from noncovalently grafted amphiphilic polymers were reported. The noncovalent amphiphilic polymers were prepared through the host-guest interaction between beta-cyclodextrin (beta-CD) grafted dextran (Dex-CD) and ferrocene (Fc) terminated poly(?-caprolactone) (PCL-Fc). Because of the presence of Fc groups, the inclusion complex between Fc and beta-CD can be reversibly controlled by an external stimulating voltage, leading to reversible formation and disassembly of the micelles. The occurrence of the inclusion complex between Fc and beta-CD was confirmed by cyclic voltammetry (CV) and the 2D NOESY spectrum. Furthermore, meloxicam was selected as a model drug to test the controlled release performance of these voltage responsive micelles. It was found that the release rate and the final cumulative release amount of meloxicam can be effectively controlled by the external voltage, which may be of use in controlled drug delivery.

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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 electrochemical, NMR, and crystallographic studies clearly indicate that the clathration and declathration of ferrocene and its derivatives in a self-assmbled Pd(II)-linked nanometer-sized cage can be controlled by the oxidation state of the guest. Namely, the guests are clathrated when they are reduced but declathrated when they are oxidized. The process is rapid on the NMR time scale but slow on the CV time scale. Copyright

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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 invention discloses a method for synthesizing amino – (N – alkyl) benzenesulfonamide method. Comprises the following steps: in the reaction container, adding amino sulfonamide, iridium complex catalyst, alkali, the compound is mellow, tertiary amyl alcohol solvent, the reaction mixture is 120 – 150o C lower reaction after several hours, cooling to room temperature, the solvent is removed by rotary evaporation, then through the column separation, to obtain the target compound. This invention uses the commercial amino sulfonamide and almost non-toxic compound alcohol starting material; only generates water as a by-product of the reaction, environmental hazard; reaction the atom economy is high. (by machine translation)

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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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Supramolecular self-assembly of molecular building blocks represents a powerful “nanoarchitectonic” tool to create new functional materials with molecular-level feature control. Here, we propose a simple method to create tunable phosphate/polyamine-based films on surfaces by successive assembly of poly(allylamine hydrochloride) (PAH)/phosphate anions (Pi) supramolecular networks. The growth of the films showed a great linearity and regularity with the number of steps. The coating thickness can be easily modulated by the bulk concentration of PAH and the deposition cycles. The PAH/Pi networks showed chemical stability between pH 4 and 10. The transport properties of the surface assemblies formed from different deposition cycles were evaluated electrochemically by using different redox probes in aqueous solution. The results revealed that either highly permeable films or efficient anion transport selectivity can be created by simply varying the concentration of PAH. This experimental evidence indicates that this new strategy of supramolecular self-assembly can be useful for the rational construction of single polyelectrolyte nanoarchitectures with multiple functionalities.

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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 report a redox-responsive liposomal system capable of oxidatively triggered disassembly. We describe the synthesis, electrochemical characterization, and incorporation into vesicles of an alternative redox lipid with significantly improved synthetic efficiency and scalability compared to a ferrocene-appended phospholipid previously employed by our group in giant vesicles. The redox-triggered disassembly of both redox lipids is examined in nanosized liposomes as well as the influence of cholesterol mole fraction on liposome disassembly and suitability of various chemical oxidants for in vitro disassembly experiments. Electronic structure density functional theory calculations of membrane-embedded ferrocenes are provided to characterize the role of charge redistribution in the initial stages of the disassembly process.

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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 isolation and characterisation of a new macrocyclic hexaamine trans-6,13-bis(ferrocenylmethylamino)-6,13-dimethyl-1,4,8,11- tetraazacyclotetradecane (L2) bearing two ferrocenyl groups appended to its exocyclic amines is reported. The crystal structures of L2 and its dihydrochloride salt L2·2HCl·2H2O have been determined. In the latter case cation-anion hydrogen bonding is observed in the solid state. Substrate binding by the electroactive L2 in MeCN-CH2Cl2 solution has been examined by cyclic voltammetry and reveals the receptor electrochemically to recognise benzoate and chloride anions. The macrocyclic N-donors may also bind transition metal cations such as CuII and ZnII.

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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 work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (beta-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by beta-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

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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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Hyphenated techniques have become an important tool in modern analytical research. Among detection techniques, mass spectrometry (MS) plays a dominant role, but efficient analyte separation prior to MS detection is usually desirable, as it provides the basis for reliable qualitative and quantitative determination. However, electrochemical methods offer very versatile approaches for selective sample pretreatment or analyte conversion. This review summarizes recent instrumental analytical developments, which resulted in a special kind of a hyphenated system: electrochemistry-capillary electrophoresis-MS (EC-CE-MS). We discuss the analytical characteristics of this approach and compare them with those of other techniques coupling EC with separation techniques and MS.

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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