Indirect Electroanalysis of 3-Methyl-4-Nitrophenol in Water Using Carbon Fiber Microelectrode Modified with Nickel Tetrasulfonated Phthalocyanine Complex

Electrochemical detection of 3-methyl-4-nitrophenol (MNP) in direct phenol oxidation occurs at high potentials and generally leads to progressive passivation of the electrochemical sensor. This study describes the use of a carbon fiber microelectrode modified with a tetrasulfonated nickel phthalocyanine complex for the detection of MNP at a lower potential than that of direct phenol oxidation. The MNP voltammogram showed the presence of an anodic peak at -0.11 V vs SCE, corresponding to the oxidation of the hydroxylamine group generated after the reduction of the nitro group. The effect of buffer pH on the peak current and SWV parameters such as frequency, scan increment, and pulse amplitude were studied and optimized to have better electrochemical response of the proposed sensor. With these optimal parameters, the calibration curve shows that the peak current varied linearly as a function of MNP concentration, leading to a limit of detection (LoD) of 1.1 μg/L. These results show an appreciable sensitivity of the sensor for detecting the MNP at relatively low potentials, making it possible to avoid passivation phenomena.

Peripheral octamethyl-substituted nickel(Ⅱ)-phthalocyanine-decorated carbon-nanotube electrodes for high-performance all-solid-state flexible symmetric supercapacitors

Construction of advanced electrode materials with unique performance for supercapacitors(SCs)is essential to achieving high implementation in the commercial market.Here,we report a novel peripheral octamethyl-substituted nickel(Ⅱ)phthalocyanine(Ni Me_(2)Pc)-based nanocomposite as the electrode material of all-solid-state SCs.The highly redox-active NiMe_(2)Pc/carboxylated carbon nanotube(CNTCOOH)dendritic nanocomposite provides rapid electron/electrolyte ion-transport pathways and exhibits excellent structural stability,resulting in high-capacity activity and impressive cycling stability.The composite prepared with the optimized weight ratio of Ni Me_(2)Pc:CNT-COOH(6:10)showed the highest specific capacitance of 330.5 F g^(-1)at 0.25 A g^(-1).The constructed NiMe_(2)Pc/CNT-COOH-based all-solid-state symmetric SC device showed excellent performance with a maximum energy density of 22.8 Wh kg^(-1)and outstanding cycling stability(111.6%retained after 35,000 cycles).Moreover,flexible carbon cloth significantly enhanced the energy density of the NiMe_(2)Pc/CNT-COOH all-solid-state symmetric device to 52.1 Wh kg^(-1)with 95.4%capacitance retention after 35,000 cycles,and it could be applied to highperformance flexible electronics applications.These findings provide a novel strategy to design phthalocyanine-based electrode materials for next-generation flexible SC devices.

Sodium-Coordinated Polymeric Phthalocyanines as Stable High-Capacity Organic Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)have attracted considerable interest as an alternative to lithium-ion batteries owing to their similar electrochemical performance and superior long-term cycle stability.Organic materials are regarded as promising anode materials for constructing SIBs with high capacity and good retention.However,utilization of organic materials is rather limited by their low energy density and poor stability at high current densities.To overcome these limitations,we utilized a novel polymeric disodium phthalocyanines(pNaPc)as SIB anodes to provide stable coordination sites for Na ions as well as to enhance the stability at high current density.By varying the linker type during a one-pot cyclization and polymerization process,two pNaPc anodes with O-(O-pNaPc)and S-linkers(S-pNaPc)were prepared,and their structural and electrochemical properties were investigated.The O-pNaPc binds Na ions with a lower binding energy compared with S-pNaPc,which leads to more facile Na-ion coordination/dissociation when engaged as SIB anode.The use of O-pNaPc significantly improves the redox kinetics and cycle stability and allows the fabrication of a full cell against Na_(3)V_(2)(PO_(4))_(2)F_(3)/C cathode,which demonstrates its practical application with high energy density(288 Wh kg^(-1))and high power density(149 W kg^(-1)).

Conjugated polymerized bimetallic phthalocyanine based electrocatalyst with Fe-N_(4)/Co-N_(4) dual-sites synergistic effect for zinc-air battery

The bifunctional oxygen catalyst is essential for zinc-air batteries(ZABs).Here,an efficient bifunctional oxygen catalyst,PPcFeCo/3D-G,is obtained throughπ-πinteraction between the conjugated polymerized iron-cobalt phthalocyanine(PPcFeCo)with excellent thermal stability and three-dimensional graphene(3D-G).The bimetallic synergistic effect of PPcFeCo,verified by DFT(Density functional theory)calculation,andπ-πinteractions enhances the catalytic activity and durability of the PPcFeCo/3D-G.Regarding electrochemical performance,the PPcFeCo/3D-G with a high electron transfer number(3.98,@0.768 V vs.RHE)has excellent half-wave potential(E_(1/2)=0.890 V vs.RHE)and exhibits outstanding reversibility(ΔE=0.700 V,ΔE=Ej=10-E_(1/2)).The liquid ZAB(LZAB)employed PPcFeCo/3D-G displays a high power density(222 m W cm^(-2)),a specific capacity(792 m A h g-1),and excellent durability(120 h).This work has guiding significance for the preparation of high-efficiency bifunctional catalysts.

Cobalt phthalocyanine-based conjugated polymer as efficient and exclusive electrocatalyst for CO_(2) reduction to ethanol

Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.

Structure of Cu-Phthalocyanine Vacuum Deposited on Inclined Glass Substrates

Cu-phthalocyanine is widely studied as a hole-transport layer in organic electronic devices. Since Cu-phthalocyanine is a molecular solid, the crystal structure depends on a circumstance to a great extent. Vacuum deposited layers were known to consist of two consecutive layers. In this article, Cu-phthalocyanine was deposited on the glass substrate inclined at several angles. The thickness of the first layer was found to be dependent on the substrate angle.

Study on the Synthesis and in vitro Photodynamic Anti-cancer Activity of Tetra(trifluoroethoxy) Germanium Phthalocyanine

The synthesis and in vitro photodynamic anticancer activity of a new photosen- sitizer, tetra（trifluoroethoxy） germanium phthalocyanine （GePcF）, were studied. GePcF was characterized by UV-Vis, IR, MS and elemental analysis. The in vitro photodynamic activity of GePcF was studied by MTT. IC50 of GePcF for SW480 cells of human colonic adenocarcinoma and HeLa cells of cervical cancer were 36.53 and 45.78 μmol/L, respectively. GePcF as a photosensitizer may be used to treat cancers due to its photodyrmmic anticancer activity.

Calculation of Visible Absorption Maxima of Phthalocyanine Compounds by Quantum Theory

Based on HYPERCHEM, the structures of five phthalocyanie compounds were optimized with PM3 and their visible absorption maxima were calculated with ZINDO/S method by selecting appropriate p-p overlap weighting factor (OWFp-p), the agreement with experiment was excellent. The relationship between OWF- and molecular structure parameters was obtained by the method of stepwise regression and was explained in terms of quantum theory. OWF-=0.58126+0.04562ANC1+0.03839X. Where, ANC1 and X are the symbols of average net charges on coordinated bonded nitrogens and electronegativity of central atom, respectively.

Synthesis and Photoconductivity of Nanosized Phthalocyanine

Functional phthalocyanine （Pc） compounds of H2Pc, TiOPc, FePc and CIAIPc were synthesized with a yield of 46.7%, 91.2%, 37.4% and 34.0%, respectively. Nanosized TiOPc was synthesized via a one-step sol-gel method and effects of surfactant doses, nucleation temperature on TiOPc particle size and photoconductivity were investigated. When re（PEG）： m（TiOPc） was 0.1 and nucleation temperature was 0℃, the as-obtained TiOPc had the smallest particle size and largest specific surface area, which were 60 nm and 83m^2/g, respectively. TiOPc synthesized under these conditions also exhibits excellent photoconductivity with charging potential V0, dark decay speed Rd and energy for half-discharging of potential E1/2 being 1160 V, 30 V/s and 0.6 1x.s, respectively.

Photogenerated carrier transfer mechanism and photocatalysis properties of TiO_2 sensitized by Zn(Ⅱ) phthalocyanine

The Zn(Ⅱ) phthalocyanine sensitized TiO2(ZnPc-TiO2) nanoparticles were prepared by hydrothermal method via impregnation with ZnPc.The as-prepared photocatalysts were characterized by X-ray diffractometry(XRD) and diffuse reflectance spectroscopy(DRS),and the surface photovoltage spectroscopy(SPS) and photocatalytic degradation of rhodamine B(RhB) were studied under illuminating.The experimental results indicate that TiO2 sensitized by ZnPc extends its absorption band into the visible region effectively,and the sensitized TiO2 has higher activity than TiO2(Degussa P-25) under the simulated solar light and the visible light.Based on the DRS and SPS results,the mechanism about the photogenerated carrier transfer between TiO2 and ZnPc is proposed.At a lower ZnPc content(≤0.20 μmol/g),ZnPc monomer acts as the electron donor,which provides the photoinduced electrons to the conduction band of TiO2.These photoinduced electrons can transfer to molecular oxygen(O2),leading to the formation of active species,such as superoxide/hydroxide radicals and singlet oxygen,which is beneficial to the photocatalytic reaction.While at a higher ZnPc content(>0.20 μmol/g),the formation of ZnPc dimer results in the decrease of photocatalytic activities of ZnPc-TiO2 photocatalyst.

First-Principles Study of Two Dimensional Transition Metal Phthalocyanine-Based Metal-Organic Frameworks in Kagome Lattice

Transition metal phthalocyanines (TMPc) and relevant derivatives can act as pervasive molecules for their electronic, magnetic, and optical applications. Numerous researches based on TMPc are carried out, attempting to synthesize novel two-dimensional (2D) metal-organic frameworks. Recently, some 2D poly-TMPc frameworks including FePc [J. Am. Chem. Soc. 133, 1203 (2011)], CoPc [Chem. Commun. 51, 2836 (2015)], and Ni-NiPc [J. Mater. Chem. A 6, 1188 (2018)] frameworks have been successfully synthesized experimentally. Meanwhile, potential applications in catalysis, gas storage, and spintronics were predicted by theoretical studies. Here, we propose a new kind of 2D poly-TMPc frameworks with kagome lattice (denoted as kag-TMPc) and systematically investigate their electronic and magnetic properties by employing first-principles calculations. We have demonstrated that the 2D kag-MnPc framework displays quite stable ferromagnetic ordering with Curie temperature about 125 K as indicated by Monte Carlo simulations based on Heisenberg model and prefers out-of-plane easy-magnetization axis. The 2D kag-CrPc framework is an ideal candidate for S=2 kagome antiferromagnet with RT3 magnetic order. Particularly, the investigations on optical absorption suggest that when the TMPc molecules are self-assembled into 2D kag- TMPc frameworks, their absorption wave bands are broadened, especially in visible region.

Studies on Metal Phthalocyanine as a Dual Functional Mimic Enzyme

Four phthalocyanines (iron tetracarboxylphthalocyanine, copper tetracarboxylphthalocyanine, manganese tetracarboxylphthalocyanine, cobalt tetracarboxylphthalocyanine) were used as dual functional mimic enzymes of superoxide dismutase (SOD) and catalase (CAT). The first function, eliminating O 2 -, was proved by using riboflavine methionine photoreduction method in the concentration range of 10 -5 to 10 -6 mol/L. The second function, clearing out H 2O 2, was demonstrated by means of spectrophotometry with the decomposing percentage being increased with the increase of the concentration of the imitating compounds. Measurements of metal phthalocyanines, SOD and CAT by the liver homogenate technique of mice showed that they had obvious action of decreasing the lipid peroxidation.

Covalent Functionalization of Carbon Nanotube by Tetrasubtituted Amino Manganese Phthalocyanine

The multiwall carbon nanotube (MWCNT) bonded to 2, 9, 16, 23-tetraamino manganese phthalocyanine (TAMnPc) was obtained by covalent functionalization, and its chemical structure was characterized by TEM. The photoconductivity of single-layered photoreceptors, where MWCNT bonded by TAMnPc (MWCNT-b-TAMnPc) served as the charge generation material (CGM), was also studied.

Enhancing Heterogeneous Catalytic Activity of Iron(II) Phthalocyanine by Ethanol and Its Application in 2,4-dichlorophenol Detection

A chemical system for facile and accurate detection of 2,4-dichlorophenol （DCP） via iron （Ⅱ） phthalocyanine （Fe（Ⅱ）Pc） catalyzed chromogenic reaction is reported for the first time. In this system, DCP could be oxidized by dioxygen with the catalysis of Fe（Ⅱ）Pc and then coupled with 4-aminoantipyrine （4-AAP） to generate pink antipyrilquinoneimine dye. Control experiments showed that the addition of ethanol could obviously enhance the catalytic activity of heterogeneous Fe（Ⅱ）Pc catalysts because of the partial dissolution of Fe（II）Pc nanocubes, which was confirmed by the SEM analysis. On the basis of the detection results of DCP in the range from 2×10^-5 to 9×10^-4 mol/L, we obtained a regression equation （A = 0.187 5 ＋ 0.01 209C （R2=-0.995 6）） with the detection limit （3σ） of 3.26×10^-6 mol/L, which could be successfully used in detecting the real samples.

Polymeric complex micelle loaded with axially substituted silicon(Ⅳ) phthalocyanine

A novel axially substituted silicon（IV） phthalocyanine, namely di-pyridyloxy axially substituted silicon（IV） phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as IH NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^e-（benzyloxycarbonyl-lysine]-poly（ethylene glycol）-poly [N^e-（benzyl oxycarbonyl） （PLL（Z）-b-PEG-b-PLL（Z）） to form hydrophobic 2-loaded polymeric complex micelle （PIC） （2-loaded P/C）. Atom force microscopy （AFM） image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced bv the incorporation 2 into PIC nanocarrier.

Tetraalkyl-substituted zinc phthalocyanines used as anode buffer layers for organic light-emitting diodes

Two soluble tetraalkyl-substituted zinc phthalocyanines(ZnPcs)for use as anode buffer layer materials in tris(8-hydroxyquinoline)aluminum(Alq3)-based organic light-emitting diodes(OLEDs)are presented in this work.The holeblocking properties of these Zn Pc layers slowed the hole injection process into the Alq3 emissive layer greatly and thus reduced the production of unstable cationic Alq3(Alq3^+)species.This led to the enhanced brightness and efficiency when compared with the corresponding properties of OLEDs based on the popular poly-(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)buffer layer.Furthermore,because of the high thermal and chemical stabilities of these Zn Pcs,a nonaqueous film fabrication process was realized together with improved charge balance in the OLEDs and enhanced OLED lifetimes.

Synthesis and photophysical properties of metal anthraquinone phthalocyanine

A novel anthraquinone phthalocyanine AI（Ⅲ） 4 and Co（Ⅱ） 5 were synthesized and characterized by elemental analysis, IR UV/ vis, ^1H NMlL HPLC and MS. The photophysical properties of the two metal complexes were studied and compared by fluorescence spectrum method.

Evaluation of Silicon Phthalocyanine 4 Photodynamic Therapy against Human Cervical Cancer Cells in Vitro and in Mice

Background: Cervical cancer is the second most common cancer in women worldwide [1]. Photodynamic therapy has been used for cervical intraepithelial neoplasia with good responses, but few studies have used newer phototherapeutics. We evaluated the effectiveness of photodynamic therapy using Pc 4 in vitro and in vivo against human cervical cancer cells. Methods: CaSki and ME-180 cancer cells were grown as monolayers and spheroids. Cell growth and cytotoxicity were measured using a methylthiazol tetrazolium assay. Pc 4 cellular uptake and intracellular distribution were determined. For in vitro Pc 4 photodynamic therapy, cells were irradiated at 667 nm at a fluence of 2.5 J/cm2 at 48 h. SCID mice were implanted with CaSki and ME-180 cells both subcutaneously and intracervically. Forty-eight hours after Pc 4 photodynamic therapy was administered at 75 and 150 J/cm2. Results: The IC50s for Pc 4 and Pc 4 photodynamic therapy for CaSki and ME-180 cells as monolayers were, 7.6 μM and 0.016 μM and >10 μM and 0.026 μM;as spheroids, IC50s of Pc 4 photodynamic therapy were, 0.26 μM and 0.01 μM. Pc 4 was taken up within cells and widely distributed in tumors and tissues. Intracervical photodynamic therapy resulted in tumor death, however mice died due to gastrointestinal toxicity. Photodynamic therapy resulted in subcutaneous tumor death and growth delay. Conclusions: Pc 4 photodynamic therapy caused death within cervical cancer cells and xenografts, supporting development of Pc 4 photodynamic therapy for treatment of cervical cancer. Support: P30-CA47904, CTSI BaCCoR Pilot Program.

Organic photovoltaic cells with copper(Ⅱ) tetra-methyl substituted phthalocyanine

Efficient heterojunction organic photovoltaic （OPV） cells are fabricated based on copper tetra-methyl phthalocyanine （CuMePc） as donor and fullerene （C60） as acceptor. The power conversion efficiency of CuMePc/C60 OPV cell （2.52%） is increased by 88% compared with that of the non-peripheral substituted copper phthalocyanine （CuPc）/C60 OPV cell （1.34%）. The introduction of methyl substituent leads to stronger π–π interaction of CuMePc （～ 3.5 ？） than that of CuPc （～ 3.8 ？）. The efficiency improvement is attributed to the enhanced carrier mobility of CuMePc thin film （1.1×10-3 cm2/V·s） and better film morphology by introducing methyl groups into the periphery of CuPc molecule.

A Fiber Optic Sensor for Determination of 2,4-dichlorophenol based on Iron(Ⅱ) Phthalocyanine Catalysis

A new fi ber optic sensor based on the oxidation of 2,4-dichlorophenol（DCP） catalyzed by iron（II） phthalocyanine（Fe（II）Pc） was developed for the determination of DCP. The optical oxygen sensing fi lm containing fl uorescence indicator Ru（bpy）3Cl2 was used to detect the consumption of oxygen in solution. Moreover, a lock-in amplifier was used to determine the lifetime of the sensor head by detecting its phase delay change. The results reveal that the sensor has a linear detection range of 1.0×10^-6- 9.0×10^-5 mol/L and a response time of 5 min. The sensor also has high selectivity, good repeatability and stability. It can be used effectively to determine DCP concentration in real samples.