Substituent engineering in g-C3N4/COF heterojunctions for rapid charge separation and high photo-redox activity

Science China Chemistry - The heterojunction constructed of covalent organic frameworks (COFs) with adjustable structure and other photocatalysts has great potential in the field of photocatalysis....     

Sub-ppt level voltammetric sensor for Hg2+ detection based on nafion stabilized l-cysteine-capped Au@Ag core-shell nanoparticles

Journal of Solid State Electrochemistry - Bimetallic nanoparticles (BMNPs) have received considerable attention due to their distinctive properties when compared to the corresponding monometallic...     

Mangostanaxanthone VIII,a new xanthone from Garcinia mangostana and its cytotoxic activity

A new prenylated xanthone, mangostanaxanthone VIII (7) and six known metabolites: gartanin (1), 1,3,8-trihydroxy-2-(3-methyl-2-butenyl)-4-(3-hydroxy-3-methylbutanoyl)-xanthone (2), rubraxanthone (3), 1,3,6,7-tetrahydroxy-8-prenylxanthone (4), garcinone C (5), and xanthone I (9-hydroxycalabaxanthone) (6) were separated from the EtOAc-soluble fraction of the air-dried pericarps of Garcinia mangostana (Clusiaceae). Their structures have been verified on the basis of spectroscopic data analysis as well as comparison with the literature. The cytotoxic activity of 7 was assessed against MCF7, A549, and HCT116 cell lines using sulforhodamine B (SRB) assay. Compound 7 showed significant cytotoxic potential against MCF7 and A549 cell lines with IC₅₀s 3.01 and 1.96 μM, respectively compared to doxorubicin (0.06 and 0.44 μM, respectively). However, it exhibited moderate activity towards HCT116 cell line.     

Preferential synthesis of highly conducting Tl(TCNQ) phase II nanorod networks via electrochemically driven TCNQ/Tl(TCNQ) solid-solid phase transformation

Facile synthesis and characterization of the highly conducting, thermodynamically favored, Tl(TCNQ) phase II microrods/nanorods onto conducting (glassy carbon (GC)) and semiconducting (indium tin oxide (ITO)) surfaces have been accomplished via redox-based transformation of 7,7,8,8-tetracynoquinodimethane (TCNQ) microcrystals. This electrochemically irreversible process involves the one-electron reduction of surface-confined solid TCNQ into TCNQ·^? with concomitant incorporation of the Tl⁺ _(aq) cation, from the bulk solution, at the triple-phase boundary, GC or ITO│(TCNQ_(s)/TCNQ·^? _(s))│Tl⁺ _(aq), through a nucleation/growth mechanism. Consistent with the conceptually related M(TCNQ) systems (M⁺ = Li⁺, Na⁺, K⁺, Ag⁺, and Cu⁺), the TCNQ/Tl(TCNQ) interconversion is strongly dependent upon scan rate, Tl⁺ _(aq) electrolyte concentration, and the method of attaching solid TCNQ onto the electrode surface. Spectroscopic (infrared (IR) and Raman), microscopic (scanning electron microscopy (SEM)), and surface science (X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD)) characterization of the electrochemically synthesized material revealed formation of pure Tl(TCNQ) phase II. Importantly, the generic solid-state electrochemical approach used in this study not only offers facile protocol for controllable and preferential synthesis of Tl(TCNQ) phase II but also provides access to fabricate and tune the morphology to yield microrod/nanorod networks.

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Graphical abstract Controlled synthesis of the highly conducting Tl(TCNQ) phase II with either nanowire or rod-like morphologies is achieved via a redox-based solid-solid phase interconversion of TCNQ microcrystals in the presence of a Tl⁺ _(aq) electrolyte.

     

Anion dependent redox changes in iron bis-terdentate nitroxide {NNO} chelates

The reaction of [Fe(II)(BF(4))(2)]·6H(2)O with the nitroxide radical, 4,4-dimethyl-2,2-di(2-pyridyl) oxazolidine-N-oxide (L(?)), produces the mononuclear transition metal complex [Fe(II)(L(?))(2)](BF(4))(2) (1) which has been investigated using temperature dependent susceptibility, Mo?ssbauer spectroscopy, electrochemistry, density functional theory (DFT) calculations, and X-ray structure analysis. Single crystal X-ray diffraction analysis and Mo?ssbauer measurements reveal an octahedral low spin Fe(2+) environment where the pyridyl donors from L(?) coordinate equatorially while the oxygen containing the radical from L(?) coordinates axially forming a linear O(?)··Fe(II)··O(?) arrangement. Magnetic susceptibility measurements show a strong radical-radical intramolecular antiferromagnetic interaction mediated by the diamagnetic Fe(2+) center. This is supported by DFT calculations which show a mutual spatial overlap of 0.24 and a spin density population analysis which highlights the antiparallel spin alignment between the two ligands. Similarly the monocationic complex [Fe(III)(L(-))(2)](BPh(4))·0.5H(2)O (2) has been fully characterized with Fe-ligand and N-O bond length changes in the X-ray structure analysis, magnetic measurements revealing a Curie-like S = 1/2 ground state, electron paramagnetic resonance (EPR) spectra, DFT calculations, and electrochemistry measurements all consistent with assignment of Fe in the (III) state and both ligands in the L(-) form. 2 is formed by a rare, reductively induced oxidation of the Fe center, and all physical data are self-consistent. The electrochemical studies were undertaken for both 1 and 2, thus allowing common Fe-ligand redox intermediates to be identified and the results interpreted in terms of square reaction schemes.     

Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization

A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ(-) monoanion. In the presence of M(x+)(MeCN), reaction with TCNQ(-)(MeCN) leads to deposition of M(x+)[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 mum in length and with diameters of less than 180 nm, and Co[TCNQ](2)(H(2)O)(2) as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal-TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.     

Synthesis of Sheet Like Nanostructures of NiO Using Potassium Dichromate as Surface Modifying Agent for the Sensitive and Selective Determination of Amlodipine Besylate (ADB) Drug

The monitoring of hypertension drugs is very critical and important to sustain a healthy life. In this study, we have synthesized nickel oxide (NiO) nanostructures using potassium dichromate as surface modifying agent by hydrothermal method. These NiO nanostructures were found highly active for the oxidation of ADB besylate (ADB). The unit cell structure and morphology were investigated by scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) techniques. The SEM study has confirmed the nano sheet like morphology and XRD analysis has described the cubic unit arrays of NiO. After the physical characterization, NiO nanostructures were used to modify the surface of glassy carbon electrode (GCE) by drop casting method. Then cyclic voltammetry (CV) was used to characterize the electrochemical activity of NiO nanostructures in the0.1 M phosphate buffer solution of pH 10.0 and a well resolved oxidation peak was identified at 0.70 V. The linear range for the NiO nanostructures was observed from 20–90 nM with a regression coefficient of 0.99 using CV. The calculated limit of detection (LOD) was 2.125 nM and the limit of quantification (LOQ) was 4.08 nM. Further to validate the CV calibration plot, an amperometry experiment was performed on the NiO nanostructures and sensors exhibited a linear range of 10 nM to 115 nM with LOD of 1.15 nM. The proposed approach was successfully used for the determination of ADB from commercial tablets and it reveals that the sensor could be capitalized to monitor ADB concentrations from pharmaceutical products. The use of potassium dichromate as a surface modifying agent for the metal oxide nanostructures may be of great interest to manipulate their crystal and surface properties for the extended range of biomedical and energy related applications.     

Highly sensitive determination of atropine using cobalt oxide nanostructures: Influence of functional groups on the signal sensitivity

This study describes sensitive determination of atropine using glassy carbon electrodes (GCE) modified with Co₃O₄ nanostructures. The as-synthesised nanostructures were grown using cysteine (CYS), glutathione (GSH) and histidine (HYS) as effective templates under hydrothermal action. The obtained morphologies revealed interesting structural features, including both cavity-based and flower-shaped structures. The as-synthesised morphologies were noted to actively participate in electro-catalysis of atropine (AT) drug where GSH-assisted structures exhibited the best signal response in terms of current density and over-potential value. The study also discusses the influence of functional groups on the signal sensitivity of atropine electro-oxidation. The functionalisation was carried with the amino acids originally used as effective templates for the growth of Co₃O₄ nanostructures. The highest increment was obtained when GSH was used as the surface functionalising agent. The GSH-functionalised Co₃O₄-modified electrode was utilised for the electro-chemical sensing of AT in a concentration range of 0.01–0.46 μM. The developed sensor exhibited excellent working linearity (R² = 0.999) and signal sensitivity up to 0.001 μM of AT. The noted high sensitivity of the sensor is associated with the synergy of superb surface architectures and favourable interaction facilitating the electron transfer kinetics for the electro-catalytic oxidation of AT. Significantly, the developed sensor demonstrated excellent working capability when used for AT detection in human urine samples with strong anti-interference potential against common co-existing species, such as glucose, fructose, cysteine, uric acid, dopamine and ascorbic acid.     

Copper vanadate nanowires-based MIS capacitors: synthesis,characterization, and their electrical charge storage applications

Dielectric properties of porous glass nanocomposites with TGS crystals embedded into six porous matrices with average pore size from 5 to 312 nm were investigated in the temperature range from 280 to 380 K at selected frequencies. The results are discussed based on the effect of the particle size on the phase transition temperature of TGS nanocomposites. Temperature–size phase diagram of TGS composites was derived. Non-monotonic character of the temperature-driven phase transition (T _p) with the decreasing particle size was determined. The nature of the T _p variation can be ascribed to the size-effect theoretically predicted by Zhong et al. (Phys Rev B 50:698–703, 1994).     

Lower Activation Energy for Catalytic Reactions through Host–Guest Cooperation within Metal–Organic Frameworks

Industrial synthesis is driven by a delicate balance of the value of the product against the cost of production. Catalysts are often employed to ensure product turnover is economically favorable by ensuring energy use is minimized. One method, which is gaining attention, involves cooperative catalytic systems. By inserting a flexible polymer into a metal–organic framework (MOF) host, the advantages of both components work synergistically to create a composite that efficiently fixes carbon dioxide to transform various epoxides into cyclic carbonates. The resulting material retains high yields under mild conditions with full reusability. By quantitatively studying the kinetic rates, the activation energy was calculated, for a physical mixture of the catalyst components to be about 50 % higher than that of the composite. Through the unification of two catalytically active components, a new opportunity opens up for the development of synergistic systems in multiple applications.