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The conjugates of porphyrin macrocycles with boron-containing polyhedra are under investigation as agents for binary treatment strategies of cancer. Aiming at the design of photoactive compounds with low-to-zero dark toxicity, we synthesized a series of carboranyl and monocarbon-carboranyl derivatives of protohaemin IX using the activation of porphyrin carboxylic groups with di-tert-butyl pyrocarbonate or pivaloyl chloride. The water-soluble 1,3,5,8-tetramethyl-2,4-divinyl-6(7)-[2?-(closo-monocarbon-carborane- 1?-yl)methoxycarbonylethyl]-7(6)-(2?-carboxyethyl)porphyrin Fe(iii) (compound 9) exerted no discernible cytotoxicity for cultured mammalian cells, nor did it cause general toxicity in rats. Importantly, 9 demonstrated dose-dependent activity as a phototoxin in photodynamic therapy of M-1 sarcoma-bearing rats. In animals injected with 20 mg kg-1 of 9, the tumours shrank by day 3 after one single irradiation of the tumour with red laser light. Between 7 and 14 days post-irradiation, 88.9% of rats were tumour-free; no recurrence of the disease was detectable within at least 90 days. Protohaemin IX alone was without effect, indicating that boronation is important for the phototoxic activity of 9. This is the first study that presents the synthesis and preclinical in vivo efficacy of boronated derivatives of protohaemin as phototoxins. The applicability in photodynamic treatment broadens the therapeutic potential of boronated porphyrins beyond their conventional role as radiosensitizers in boron neutron capture therapy. The Royal Society of Chemistry 2006.

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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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Supramolecular encapsulation is known to alter chemical properties of guest molecules. We have applied this strategy of molecular encapsulation to temporally control the catalytic activity of a stable copper(I)?carbene catalyst. Encapsulation of the copper(I)?carbene catalyst by the supramolecular host cucurbit[7]uril (CB[7]) resulted in the complete inactivation of a copper-catalyzed alkyne?azide cycloaddition (CuAAC) reaction. The addition of a chemical signal achieved the near instantaneous activation of the catalyst, by releasing the catalyst from the inhibited CB[7] catalyst complex. To broaden the scope of our on-demand CuAAC reaction, we demonstrated the protein labeling of vinculin with the copper(I)?carbene catalyst, to inhibit its activity by encapsulation with CB[7] and to initiate labeling at any moment by adding a specific signal molecule. Ultimately, this strategy allows for temporal control over copper-catalyzed click chemistry, on small molecules as well as protein targets.

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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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Graphene quantum dots (GQDs) – zero-dimensional materials – are sheets of a few nanometers in lateral dimension and exhibit quantum confinement and edge site effects where sp2-bonded carbon nanocore surrounded with edged plane functional moieties is promising as advanced electroactive sensing platforms. In this work, GQDs are synthesized by solvothermal and hydrothermal techniques, with optimal size of 5 nm. Their potential in fundamental (direct electron transfer) and applied (enzymatic glucose biosensor) electrochemistry are demonstrated. Glucose oxidase (GOx) immobilized on glassy carbon (GC) electrodes modified with GQDs are investigated by means of cyclic voltammetry, differential pulse voltammetry, and amperometry. Well-defined quasi-reversible redox peaks observed under various electrochemical parameters helped to determine diffusion coefficient (D) and first-order electron transfer rate (kET). The cyclic voltammetry curves showed homogeneous ion transport for GQD with D ranging between 8.45 × 10-9 m2 s-1 and 3 × 10-8 m2 s-1 following GO < rGO < GQD < GQD (with FcMeOH as redox probe) < GOx/rGO < GOx/GO < HRP/GQDs < GOx/GQDs. The developed GOx-GQDs biosensor responds efficiently and linearly to the presence of glucose over concentrations ranging 10 muM and 3 mM with limit of detection 1.35 muM and sensitivity 0.00769 muA muM-1·cm-2 as compared with rGO (0.025 muA muM-1 cm-2, 4.16 muM) and GO (0.064 muA muM-1 cm-2, 4.82 muM) nanosheets. The high performance and stability of GQDs is attributed to sufficiently large surface-to-volume ratio, excellent biocompatibility, abundant hydrophilic edge site density, and partially hydrophobic planar sites that favors GOx adsorption on the electrode surface and versatile architectures to ensure rapid charge transfer and electron/ion conduction (<10 ms). We also carried out similar studies with other enzymatic protein biomolecules on electrode surfaces prepared from GQD precursors for electrochemical comparison, thus opening up potential sensing applications in medicine as well as bio-nanotechnology. Therefore, this conceptually novel strategy might open impressive avenues to establish green and sustainable chemistry platforms. In my other articles, you can also check out more blogs about 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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Hierarchical porous gold films with a well-defined bimodal architecture have been made by electrodepositing gold at a constant current around a close-packed assembly of raspberry-like latex spheres (1200/60 nm) followed by template removal. Electrodeposition was stopped when the gold was either layer or 1 layer thick as evident from oscillations in the potential vs time traces. Scanning electron microscopy (SEM) images show the hierarchical pore structure with an ensemble of small ?20 nm openings located in a large ?1200 nm diameter macropore. Prior to electrochemical characterization, the electrodes were cleaned either chemically and/or via UV radiation and X-ray photoelectron spectroscopy (XPS) was used to evaluate the presence of residual polystyrene. Of the three cleaning methods investigated, sonication in chloroform-acetone followed by UV radiation proved best. The surface area of the hierarchical porous gold electrodes, determined by integrating the area under the gold oxide peak, was 4× larger than a bare gold electrode and 2× larger than a macroporous gold electrode prepared using unimodal, 1200 nm diameter latex spheres as the template. The electrochemical performance of the electrodes relative to the macroporous gold and flat gold was undertaken using cyclic voltammetry. The results show that the non-Faradaic current scales linearly with electrode area while the Faradaic current of a diffusing electrochemically reversible redox probe (ferrocene methanol) does not. For an adsorbed redox couple (ferrocene hexanethiol), the voltammetric wave shapes and surface coverage were different for the different electrodes.

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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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In this work, a novel redox capacitor was designed for signal amplification in electrochemical detection. It was fabricated by co-electrodeposition of a conducting polymer, sulfonated polyaniline (SPAN) and chitosan on a glass carbon electrode, and its function was evaluated for being a localized source to transfer electron between FcCOOH (Fc) and Ru(NH3)6Cl3 in solution via redox cycling. Furthermore, the electrochemical detection of chloramphenicol, a broad-spectrum antibiotic was performed using the redox capacitor in the presence of Fc. A significant amplification in cathodic current response of chloramphenicol was obtained through a continuous redox-cycling reaction. The performance of the amplifying signal responded linearly to chloramphenicol in a concentration range of 0.05 to 50.0 mumol L?1 with a low detection limit of 0.01 mumol L?1. The proposed approach exhibited good reproducibility and stability, and could be used for detection of chloramphenicol in eye drops by standard addition method with the recoveries from 96.5 % to 103.0 %.

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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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Reaction of ferrocenylmethanol, FcCH2OH, with beta-cyano-N,N-diisopropyl chlorophosphoramidite in dichloromethane yields the ferrocenylmethylphosphonate derivative, FcCH2P(O)(N(iPr)2)(OCH2CH2CN), 2a. The crystal and molecular structure of 2a is presented. 31P NMR data suggest that this is formed from FcCH2OP(N(iPr)2)(OCH2CH2CN) via a Michaelis-Arbusov-type rearrangement. Similar behaviour was also observed for 1,2-phenylene chlorophosphite and diethyl chlorophosphite.

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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 synthesis of a C2 symmetric 1,1? ,2,2?-tetrasubstituted ferrocene system was discussed. The route involved the reduction of ferrocenyl carbonyl compounds which gave access to a range of alcohols, alkenes, alkanes, ethers, and 2-oxa[3]ferrocenophanes depending on the precise conditions used. The loss of optical activity of 1,1?-bis(hydroxymethyl)ferrocenes and 1,1?-bis(hydroxymethyl)ruthenocenes, which had been prepared by asymmetric reduction, was demonstrated in an acidic medium by extensive 1H NMR studies.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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In this work, a novel “signal on” photoelectrochemistry (PEC) biosensor was constructed with dual-functional hemin as a signal quencher and electronic mediator for ultrasensitive target microRNA-141 assay with the assistance of T7 exonuclease (Exo)-initiated target amplification technology.

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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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Synthesis, structure determination and in vitro antiproliferative assay of a series of novel ferrocenenyl hydrazones containing 4-halopyridazin-3(2H)-one fragment(s) and three representative N-arylsubstituted (Sp)-ferroceno[d] pyridazinones are presented. The model compounds can be considered as different assemblies of the potential binding sites capable of establishing interactions including hydrogen bonds and pi-pi interactions with the relevant residues of biomolecules. Their in vitro antiproliferative effect was investigated against four tumorous cell lines by the 3-(4,5-dimethylthiazol-2-yl)-2,5- diphenyltetrazolium bromide (MTT)-assay. Our data indicate that bis-hydrazone of 1,1?-diformylferrocene carrying N-benzyl substituents and a chloropyridazinyl-substituted ferroceno[d]pyridazinone display significant activity on each cell lines investigated. The efficiency of the latter drug candidate and one N-benzyl mono-hydrazone on A2870 cell line is comparable to that of cisplatin. The constitution and relative configuration of the model compounds were established by 1H, 13C and 15N NMR methods. The structures of a mono- and bis-ferrocenylhydrazone containing 4-bromopyridazinone unit(s) were confirmed by single crystal X-ray diffraction.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
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Condensation reaction of 1,1?-ferrocenedicarboxaldehyde with (1R,2R)-1,2-diaminocydohexane affords a novel bowl-shaped macrocycle with a chiral concave cavity which exhibits a remarkable ability as a host material for the enantioselective enclathration of 1,1?-bi-2-naphthol.

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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