Ferrous Phthalocyanine Research Articles

Elimination of mutagenic contaminants from water using cellulose bearing ferrous-phthalocyanine

BackgroundWe previously investigated methods for separating mutagenic contaminants from aqueous solutions using cellulose-bearing covalently bound trisulfo-Cu-phthalocyanine (blue cotton and blue rayon). Mutagenic contaminants with three or more fused aromatic rings in their structures were adsorbed onto blue cotton and rayon. Since Cu-phthalocyanine is considered an unsuitable absorption ligand for byproducts of water chlorination, such as 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (Mutagen X or MX), we investigated the development of a new material for the elimination of MX from aqueous solvents.ResultsWe selected green cellulose powder bearing ferrous phthalocyanine (FePh), hereafter referred to as green cellulose or GP, as the candidate material. GP is composed of cationized cellulose (white cellulose, WP) and FePh tetracarboxylic acid. The mutagenicity of MX dissolved in buffer or dimethyl sulfoxide (DMSO) solution significantly decreased after treatment with GP. The effects of GP on the elimination of MX from the solvent were very close to being expired after 70 cycles of repeated adsorption of the same GP, and the capacity of GP for MX removal was estimated to be exhausted after 120 cycles of repeated adsorption based on the extrapolation of the obtained result; thus, the interacting ligands on GP may be saturated after complete MX adsorption. The mutagenicity of MX dissolved in aqueous buffer significantly decreased after treatment at pH7.4 but not at pH 4.0. Since MX is dissociated to be the anionic form at pH 6 or higher, the negative charge of MX in the buffer at pH 7.4 may interact with the positive charge of ferrous ions in GP to create a linkage between MX and GP. After GP adsorbed MX, mutagenicity was extracted with water or acetonitrile and recovered in the eluent. Thus, the reversible interaction between MX and FePh may have caused adsorption of MX onto GP.ConclusionGP could be used as a new eliminator and recovery agent for MX in chlorinated drinking water. Developing new materials for the removal and recovery of agents for the detection of mutagenic contaminant-related chlorination in water is beneficial for environmental health.

An anti-fouling surface molecularly imprinted ratiometric electrochemical biosensor for SARS-CoV-2 spike protein

An anti-fouling surface molecularly imprinted (SMI) ratiometric electrochemical biosensor was fabricated for the detection of severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) spike protein (S protein). Polypyrrole (PPy) was electrodeposited on the electrode surface by using ferrous phthalocyanine (PcFe) and sodium alginate (SA) as the dopants, which acted as the molecularly imprinted polymers (MIPs). The SMI electrochemical biosensor could be used for the detection of SARS-CoV-2 S protein based on the ratiometric signals of the internal reference (PcFe) and the external probe ([Fe(CN)6]3−/4−). Under optimized conditions, the as-fabricated SMI ratiometric biosensor showed a wide linear range of 100 fg mL−1 ∼ 100 ng mL−1 with a low limit of detection (LOD) of 30.1 fg mL−1. Nonspecific adsorption of interfering substances onto the SMI biosensor surface could be significantly reduced due to the outstanding anti-fouling ability of SA, as revealed by fluorescence microscopy. Finally, the reliability of the SMI ratiometric electrochemical biosensor was demonstrated by the detection of SARS-CoV-2 S protein in clinical serum samples. The findings of this work open a new avenue in clinical diagnosis of COVID-19.

Atomic Fingerprinting of Heteroatoms Using Noncontact Atomic Force Microscopy.

Immense strides have been made in increasing the resolution of scanning probe microscopy. Noncontact atomic force microscopy (nc-AFM) now offers one the ability to characterize and visualize single molecules with subatomic resolution. Specifically, nc-AFM with a carbon monoxide (CO) functionalized tip has the ability to discriminate functional groups (-CC-, -CH2 , -CO, …), although discriminating atomic species often remains as an ongoing challenge. Here, real-space pseudopotentials constructed within density functional theory are employed to accurately simulate nc-AFM images of molecules containing heteroatoms (S, I, and N) within dibenzothiophene (DBT), 2-iodotriphenylene (ITP), acridine (ACR) and ferrous phthalocyanine (FePc). It is found that S and I atoms can be easily identified from C based on their unique features. For N atoms, a use of tip functionalization is proposed to effectively discriminate them from C atoms.

Breaking a dative bond with mechanical forces

Bond breaking and forming are essential components of chemical reactions. Recently, the structure and formation of covalent bonds in single molecules have been studied by non-contact atomic force microscopy (AFM). Here, we report the details of a single dative bond breaking process using non-contact AFM. The dative bond between carbon monoxide and ferrous phthalocyanine was ruptured via mechanical forces applied by atomic force microscope tips; the process was quantitatively measured and characterized both experimentally and via quantum-based simulations. Our results show that the bond can be ruptured either by applying an attractive force of ~150 pN or by a repulsive force of ~220 pN with a significant contribution of shear forces, accompanied by changes of the spin state of the system. Our combined experimental and computational studies provide a deeper understanding of the chemical bond breaking process.

Biomimetic Au/CeO2 Catalysts Decorated with Hemin or Ferrous Phthalocyanine for Improved CO Oxidation via Local Synergistic Effects.

SummaryBiomimetic catalysts have drawn broad research interest owing to both high specificity and excellent catalytic activity. Herein, we report a series of biomimetic catalysts by the integration of biomolecules (hemin or ferrous phthalocyanine) onto well-defined Au/CeO2, which leads to the high-performance CO oxidation catalysts. Strong electronic interactions among the biomolecule, Au, and CeO2 were confirmed, and the CO uptake over hemin-Au/CeO2 was roughly about 8 times greater than Au/CeO2. Based on the Au/CeO2(111) and hemin-Au/CeO2(111) models, the density functional theory calculations reveal the mechanisms of the biomolecules-assisted catalysis process. The theoretical prediction suggests that CO and O2 molecules preferentially bind to the surface of noncontacting Au atoms (low-coordinated sites) rather than the biomolecule sites, and the accelerating oxidation of Au-bound CO occurs via either the Langmuir-Hinshelwood mechanism or the Mars-van Krevelen mechanism. Accordingly, the findings provide useful insights into developing biomimetic catalysts with low cost and high activity.

Replacement reactions at a ferrous phthalocyanine centre. Piperidine and substituted pyridines as entering ligands

Using the recent Wye Memorandum negotiations between Israelis and Palestinians as a case example, the author applies a framework for analyzing momentum-building processes previously presented in the July 1998 issue of the journal. Focusing on the impact of action-forcing events, be examines the factors that led the parties to come to the table at Wye and to make the bard choices necessary to reach agreement. The Wye example illustrates that action-forcing events can both help to build momentum and erect additional barriers to agreement.

LIGAND REPLACEMENT REACTIONS OF FERROUS PHTHALOCYANINE IN DIMETHYLSULPHOXIDE : CONFIRMATION THAT BOTH STEPS CAN BE OBSERVED

Reactions of ferrous phthalocyanine with 4–aminopyridine, imidazole or pyridine in dimethylsulphoxide have been re-investigated using exacting stopped-flow techniques focusing attention on the rapid first stage forming the intermediate FePc(dmso)(base). Effects of impurities in ferrous phthalocyanine samples formed during storage, and the presence of μ-oxo dimer, on the observed kinetic behaviour with base were examined. The correctness of the findings of an Italian group that kinetic data can be obtained for the first step was affirmed. New results and reassigned published data enabled rate and equilibrium constants to be assigned to the first and second steps for reactions of ferrous phthalocyanine with each of the three nitrogenous bases employed.

Photoconductivity of phthalocyanine composites II: Double-layered photoreceptor of Fe IIPcPVK

The photoconductivities of double-layered photoreceptors, containing ferrous phthalocyanine (Fe IIPc) and other phthalocyanines as charge generator and polyvinylcarbazole as charge transporter, were studied. The results show an increased photoconductivity of Fe IIPcAlClPc, Fe IIPcNdPc and Fe IIPcMnPc compared with the pure phthalocyanines, but a decreased photoconductivity of Fe IIPcInClPc. In these composites, polymorphic transformation of Fe IIPc occurs and its molecular interaction changes.

Bonding of nitrosobenzene and phenyl isocyanide to chelated mesoheme, hemoglobin and ferrous phthalocyanine

Reactions of nitrosobenzene, phenyl isocyanide and their ring-substituted analogues with hemoglobin, ferrous phthalocyanine and a synthetic model compound of hemoglobin were investigated by optical, 1H-NMR and infrared spectroscopy. Complexes of chelated ferromesoheme, the model compound, with 2-methyl-, 2-ethyl-, 2-isopropyl- or 2,6-disubstituted nitrosobenzene were less stable than its complex with nitrosobenzene. Formation of a complex of the model compound with 2- tert-butylnitrosobenzene was incomplete. Previous studies showed that 2,6-disubstituted nitrosobenzenes are not ligands of ferrohemoglobin. In the present work 2,6-dimethylphenyl isocyanide was found to be a ligand of ferrohemoglobin. These results are consistent with binding of the nitrogen of the nitroso group of nitrosobenzene and of the carbon of the isocyanide group of phenyl isocyanide to ferroheme. The same bonding modes of these ligands to ferrous phthalocyanine were inferred from ring-current-induced shifts in the 1H-NMR spectra of the respective complexes.

Kinetics and equilibriums for benzyl isocyanide binding to ferrous phthalocyanine complexes

Kinetics and equilibriums for benzyl isocyanide binding to ferrous phthalocyanine complexes

Isotope Effect of Iron Recoil Atoms in Ferrous Phthalocyanine

Isotope Effect of Iron Recoil Atoms in Ferrous Phthalocyanine

Complexes of ferrous phthalocyanine with aromatic nitroso compounds, isocyanides, and phosphites

Complexes of ferrous phthalocyanine with aromatic nitroso compounds, isocyanides, and phosphites

Reaction of N-substituted imidazoles with ferrous phthalocyanine in dimethylsulphoxide

Reaction of N-substituted imidazoles with ferrous phthalocyanine in dimethylsulphoxide

Letter: Complexes of benzyl isocyanide with ferrous phthalocyanine. A model for the heme group and a solar energy storage system.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTComplexes of benzyl isocyanide with ferrous phthalocyanine. Model for the heme group and a solar energy storage systemDennis V. StynesCite this: J. Am. Chem. Soc. 1974, 96, 18, 5942–5943Publication Date (Print):September 1, 1974Publication History Published online1 May 2002Published inissue 1 September 1974https://doi.org/10.1021/ja00825a045RIGHTS & PERMISSIONSArticle Views98Altmetric-Citations24LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (282 KB) Get e-Alerts Get e-Alerts

Kinetics and equilibria for carbon monoxide binding to ferrous phthalocyanine complexes.

Kinetics and equilibria for carbon monoxide binding to ferrous phthalocyanine complexes.

Effect of Pressure on the Electronic Structure of Phthalocyanine and Iron Phthalocyanine Derivatives

The electronic structures of phthalocyanine, ferrous phthalocyanine, and the adducts with pyridine, 3-picoline, 4-picoline, and piperidine have been studied to 175 kbar pressure using optical absorption and Mössbauer resonance. One observes shifts of the optical absorption peaks to lower energy and changes in relative intensity of peaks which can be explained in terms of changes in the configuration interaction. Fe(II) in ferrous phthalocyanine is in an intermediate spin configuration at all pressures. In the axially coordinated adducts the Fe(II) is low spin at 1 atm. For the pyridine and picoline adducts this is caused by the increased backbonding to the axial ligands in addition to the phthalocyanine and by repulsion due to σ bonding. These factors both tend to separate the dz2 orbitals from the dπ orbitals. In the piperidine adduct only the latter factor is operative. With increasing pressure the low spin compounds convert partially to a new spin state, believed to be intermediate spin. The picolines show the most conversion, the pyridine adduct less, and the piperidine complex still less. The general explanation lies in the decrease in backbonding at high pressure caused by the tendency for occupation of the ligand π* orbitals by ligand π electrons. A similar effect has been observed in ferrocyanides and in phenanthroline complexes. The differences among the various adducts can be explained in terms of differences in the degree of π backbonding and σ bonding.

The reaction of hydrochloric acid with ferrous phthalocyanine

The reaction of hydrochloric acid with ferrous phthalocyanine

Replacement of dimethyl sulfoxide by imidazole at the axial sites of ferrous phthalocyanine. II.

Investigation on the replacement of d.m.s.o by Imidazole at a Ferrous phthalocyanine centre have been extended over six-thousand fold range of Imidazole concentration by using the stopped-flow method. The observed rate constant is still directly proportional to Imidazole concentration even at the highest (1.45 M) Imidazole concentrations, so that no experimental support for a limiting SN1 mechanism has been obtained. Reasons are presented to show that such a mechanism is not ruled out, but experimental support must now be sought in other solvent/nucleophile combinations with ferrous phthalocyanine.

An adduct of hydrogen bromide and ferrous phthalocyanine

Ferrous phthalocyanine (FePc) and concentrated hydrobomic acid react giving a 1:1 FePc-HBr adduct. In aprotic solvents adduct formation is reversable and is a reaction of bromide ion with protonated phthalocyanine.

The nature of ‘chloroferric phthalocyanine’

Experiments in dimethyl sulphoxide and dimethylacetamide show that ‘chloroferric phthalocyanine’ is most probably a hydrochloride of ferrous phthalocyanine. Evidence is presented to show that chloride ion is acting as an axial ligand at a ferrous centre. The proton modifies the phthalocyanine ring, presumably being attached to an azomethine bridge. These results are discussed in the light of previous ones.