Novel axially carborane-cage substituted silicon phthalocyanine photosensitizer; synthesis, characterization and photophysicochemical properties

NASA Astrophysics Data System (ADS)

Atmaca, Göknur Yaşa; Dizman, Cemil; Eren, Tarık; Erdoğmuş, Ali

2015-02-01

The novel axially dicarborane substituted silicon (IV) (SiPc-DC) phthalocyanine was synthesized by treating silicon phthalocyanine dichloride SiPc(Cl)2 (SiPc) with o-Carborane monool. The compound was characterized by mass spectrometry, UV-Vis, FT-IR, 1H and 11B Nuclear Magnetic Resonance Spectroscopy (NMR). Spectral, photophysical (fluorescence quantum yield) and photochemical (singlet oxygen (ΦΔ) and photodegradation quantum yield (Φd)) properties of the complex were reported in different solutions (Dimethyl sulfoxide (DMSO), Dimethylformamide (DMF) and Toluene). The results of spectral measurements showed that both SiPc and carborane cage can have potential to be used as sensitizers in photodynamic therapy (PDT) and boron neutron capture therapy (BNCT) by their singlet oxygen efficiencies (ΦΔ = 0.41, 0.39).

Aldehyde Substituted Phthalocyanines: Synthesis, Characterization and Investigation of Photophysical and Photochemical Properties.

PubMed

Sen, Pinar; Yildiz, S Zeki; Erdoğmuş, Ali; Dege, Necmi; Atalay, Yusuf

2016-07-01

The new free and nickel phthalocyanine derivatives, tetrakis [(2-formylphenoxy)-phthalocyanine (4), tetrakis [(2-formylphenoxy)-phthalocyaninato]nickel(II) (5) have been synthesized via de-protection of tetra acetal-substituted phthalocyanines in acetic acid/FeCl3 system. The starting phthalocyanines, tetrakis [(2-(1,3-dioxolan-2-yl)phenoxy)-phthalocyanine (2) and tetrakis [(2-(1,3-dioxolan-2-yl)phenoxy)-phthalocyaninato]nickel (3), were prepared by the tetramerization of 4-(2-(1,3-dioxolan-2-yl) phenoxy) phthalonitrile (1). The new compounds have been characterized by the combination of FT-IR, (1)H NMR, UV-Vis, Mass spectra and elemental analysis. Compound 1 crystallizes in the Orthorhombic, space group Pbca with a = 9.2542 (4) Å, b = 13.3299 (5) Å, c = 23.2333 (11) Å, and Z = 8. Compound 1 is built up from two planar groups (phthalonitrile and phenoxy), with a dihedral angle of 69.693(36)° between them and non-planar dioxolane group. We report a combined experimental and theoretical study on molecule 1, as well. Geometric, spectroscopic and electronic properties of compound 1 has been calculated using B3LYP method and 6-311++G(dp) basis set. Fluorescence spectroscopy was applied to record the photoluminescence spectra of the prepared phthalocyanines and the photophysical and photochemical properties were examined in DMSO.

Synthesis and characterization of tetra phenoxy-substituted halogen-rich metallophthalocyanine derivatives: A study on their LCD color filter requirements

NASA Astrophysics Data System (ADS)

Muthukumar, Palanisamy; Kim, Hak-Soo; Jeong, Jong Woo; Son, Young-A.

2016-09-01

This study addresses the synthesis and characterization of new tetra phenoxy-substituted halogen-rich metallophthalocyanine derivatives (MPcs) 4-7 (M = Co, Ni, Cu and Zn). The synthesized new compounds were characterized using UV-Vis, FT-IR, MALDI-TOF, 1H NMR and elemental analyses. In addition, the basic requirements such as aggregation behavior, thermal stability, transmittance and solubility in propylene glycol monomethyl ether acetate (PGMEA) of MPcs 4-7 were investigated for their usage as a green color filter in Liquid Crystal Displays (LCDs). All of the MPcs showed thermal stability and sufficient solubility in PGMEA. However, the addition of binder into PGMEA solution of MPcs 5 and 6 leads to precipitation. Among the four MPcs, zinc phthalocyanine (7) showed higher transmittance. The higher transmittance of zinc phthalocyanine (7) along with its thermal stability and sufficient solubility in PGMEA are promising for its application as a green color filter in LCDs.

Regioisomer-Free C 4h β-Tetrakis(tert-butyl)metallo-phthalocyanines: Regioselective Synthesis and Spectral Investigations.

PubMed

Iida, Norihito; Tanaka, Kenta; Tokunaga, Etsuko; Takahashi, Hiromi; Shibata, Norio

2015-04-01

Metal β-tetrakis(tert-butyl)phthalocyanines are the most commonly used phthalocyanines due to their high solubility, stability, and accessibility. They are commonly used as a mixture of four regioisomers, which arise due to the tert-butyl substituent on the β-position, and to the best of our knowledge, their regioselective synthesis has yet to be reported. Herein, the C 4h -selective synthesis of β-tetrakis(tert-butyl)metallophthalocyanines is disclosed. Using tetramerization of α-trialkylsilyl phthalonitriles with metal salts following acid-mediated desilylation, the desired metallophthalocyanines were obtained in good yields. Upon investigation of regioisomer-free zinc β-tetrakis(tert-butyl)phthalocyanine using spectroscopy, the C 4h single isomer described here was found to be distinct in the solid state to zinc β-tetrakis(tert-butyl)phthalocyanine obtained by a conventional method.

Formation, characterization, aggregation, fluorescence and antioxidant properties of novel tetrasubstituted metal-free and metallophthalocyanines bearing (4-(methylthio)phenoxy) moieties

NASA Astrophysics Data System (ADS)

Yıldırım, Nurdan; Bilgiçli, Ahmet T.; Alici, Esma Hande; Arabacı, Gulnur; Yarasir, M. Nilüfer

2017-09-01

The synthesis and characterization of peripherally tetra 4-(methylthio)phenoxy substituted metal-free(2), Zn(II) (3) and Co(II) (4) phthalocyanine derivatives were reported. These newly synthesized phthalocyanine derivatives showed the enhanced solubility in organic solvents and they were characterized by a combination of elemental analysis, FTIR, 1H NMR, 13C NMR, UV-vis and MALDI-TOF/MS spectral data. Their aggregation properties were investigated in THF by UV-vis and fluorescence. These metal-free and metallophthalocyanine compounds were also evaluated for their total antioxidant abilities by using three different antioxidant methods such as 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging, ferrous ion chelating and reducing power activity. All tested compounds showed radical scavenging activity. The highest radical scavenging activity was found from cobalt phthalocyanine (4) compound respectively. IC50 values of the compounds and standards (BHT and Trolox) were also determined. The results showed that the compound 4 had the highest antioxidant activity among all tested compounds including standards. The tested phthalocyanine compounds had ferrous ion chelating activity. In addition, they showed very high reducing power. All tested compounds had higher reducing power than the standards such as ascorbic acid and BHT. The present study shows that the synthesized tetra phthalocyanine [M: 2H(2), Zn(II)(3), Co(II)(4)] with four peripheral 4-(methylthio) phenoxy compounds have the effective antioxidant properties that can be used as antioxidant agents.

Novel homo- and heterobinuclear ball-type phthalocyanines: synthesis and electrochemical, electrical, EPR and MCD spectral properties.

PubMed

Odabaş, Zafer; Dumludağ, Fatih; Ozkaya, Ali Riza; Yamauchi, Seigo; Kobayashi, Nagao; Bekaroğlu, Ozer

2010-09-21

The mononuclear Fe(II) phthalocyanine 2 and ball-type homobinuclear Fe(II)-Fe(II) and Cu(II)-Cu(II) phthalocyanines, 3 and 4 respectively, were synthesized from the corresponding 4,4'-[1,1'-methylenebis-(naphthalene-2,1-diyl)]bis(oxy)diphthalonitrile 1, and then ball-type heterobinuclear Fe(II)-Cu(II) phthalocyanine 5 was synthesized from 2. The novel compounds 4 and 5 have been characterized by elemental analysis, UV/vis, IR and MALDI-TOF mass spectroscopies. Electron paramagnetic resonance and magnetic circular dichroism measurements of 3, 4 and 5 were also examined. The voltammetric measurements of the complexes showed the formation of various electrochemically stable ligand- and metal-based mixed-valence species, due to the intramolecular interactions between the two MPc units, especially in ball-type binuclear iron(II) phthalocyanine. Impedance spectroscopy and d.c. conductivity measurements of 4 and 5 were performed as a function of temperature (295-523 K) and frequency (40-10(5) Hz). While room temperature impedance spectra consist of a curved line, a transformation into a full semicircle with increasing temperature was observed for both compounds.

Synthesis and characterization of novel 4-Tetra-4-Tolylsulfonyl ZnPc thin films for optoelectronic applications

NASA Astrophysics Data System (ADS)

Khalil, Salah; Tazarki, Helmi; Souli, Mehdi; Guasch, Cathy; Jamoussi, Bassem; Kamoun, Najoua

2017-11-01

Novel 4-Tetra-4-Tolylsulfonyl:zinc phthalocyanine and simple zinc phthalocyanine were synthesized. Our materials were grown on glass substrates by spin coating technique. Thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electronic micrograph (SEM), atomic force microscopy (AFM), spectrophotometer and Hall effect measurement. X-ray spectra reveal that 4-Tetra-4-Tolylsulfonyl:zinc phthalocyanine (4T4TS:ZnPc) and zinc phthalocyanine (ZnPc) thin films have a monoclinic crystalline structure in β phase. The surface properties and chemical composition were detailed using XPS measurement. SEM were used to investigate the surface morphology for 4T4TS:ZnPc and ZnPc thin films. Atomic force microscopy images have shown a decrease in surface roughness after substitution. Optical properties were investigated by measuring transmission and reflection spectra. Electrical properties were studied and the different electrical parameters was measured and compared on glass, silicon and tin dioxide substrates by Hall Effect technique. All obtained results indicate an improvement in physical properties of 4T4TS:ZnPc which allows used it in optoelectronic applications.

Development of Smart Phthalocyanine-based Photosensitizers for Photodynamic Therapy

NASA Astrophysics Data System (ADS)

Chow, Yun Sang

Phthalocyanines are versatile functional dyes that have shown great potential in cancer theranostics, especially in photodynamic therapy (PDT). This research work aims to develop "smart" phthalocyanine-based photosensitizers for targeted PDT. This thesis describes the synthesis, spectroscopic characterization, photophysical properties, and in vitro photodynamic activities of several series of carefully designed phthalocyanine-based photosensitizers. Chapter 1 presents an overview of PDT, including its historical development, photophysical mechanisms, and biological mechanisms. Various classes of photosensitizers are introduced with emphasis putting on phthalocyanines, which exhibit ideal characteristics of photosensitizers for PDT. In recent years, several approaches have been used to develop photosensitizers with higher tumor selectivity and minimal skin photosensitivity after PDT. Activatable photosensitizers can provide a "turn on" mechanism to offer an additional control of the specificity of treatment. Photosensitizers can also work cooperatively with the tumor-targeting groups or anticancer drugs so as to achieve targeted or dual therapy, which can enhance the efficacy of PDT. The novel approaches mentioned above have been widely used and combined to form multi-functional photosensitizing agents. These novel concepts and development of PDT are discussed and illustrated with relevant examples at the end of this chapter. To minimize the prolonged skin photosensitivity, photosensitizers that can only be activated by tumor-associated stimuli have been developed. Due to the abnormal metabolism in tumor tissues, their surface usually exhibits a lower pH compared to that of the normal tissues. Also, the pH difference between the intracellular and the physiological environment provides a pH-activation mechanism. Chapter 2 presents the synthesis and spectroscopic characterization of a pH-responsive zinc(II) phthalocyanine tetramer, in which the phthalocyanine units are self-quenched, but separated and activated after cleavage of the acetal linkages. The basic photophysical properties, activation behavior in fluorescence emission, singlet oxygen generation, and in vitro photodynamic activities of this compound have been investigated and compared with those of the non-cleavable analogue. The activation of this tetramer has been demonstrated in the aqueous medium and at the cellular level, in which the fluorescence emission and photosensitizing ability can be greatly enhanced. This tetramer exhibits low dark toxicity and enhanced cytotoxicity upon illumination toward the HT29 human colon adenocarcinoma cells. Glutathione (GSH) is another well-documented stimulus for the design of activatable photosensitizers. It is the most abundant biological thiol which acts as the reducing agent in many biochemical processes. The much higher intracellular GSH concentration compared with the extracellular GSH level provides an activation mechanism. By using this feature, we have developed a series of GSH-responsive phthalocyanine dendrons in order to optimize the molecular design of self-quenched activatable photosensitizers. The aggregation tendency and the activation behavior in fluorescence emission and singlet oxygen generation in aqueous media have been investigated. The in vitro properties of the phthalocyanine dendrons including relative intracellular fluorescence and photocytotoxicity are also examined and presented in Chapter 3.. Chapter 4 reports the molecular design and synthesis of a biotin-decorated GSH-responsive zinc(II) phthalocyanine trimer, in which the phthalocyanine units are severely self-quenched, but are separated and then activated upon cleavage of the disulfide bondings by GSH. The basic photophysical properties, cleavage kinetics, and activation behavior in fluorescence and photosensitizing ability of this compound have been investigated. Its in vitro photodynamic activity, cellular uptake by different cell lines, and intracellular fluorescence emission have also been examined. Apart from targeted PDT, dual therapy is another novel approach to improve the efficacy of PDT treatment. Chapter 5 describes the molecular design and synthesis of a novel doxorubicin-conjugated phthalocyanine trimer. Doxorubicin is a well-known drug for the treatment of a range of cancers. By conjugating this unit to a GSH-responsive zinc(II) phthalocyanine trimer, it is expected that the resulting hybrid can exhibit controlled toxicity. The basic photophysical properties and effects of GSH on the fluorescence emission and photosensitizing ability of this compound have been investigated. Its cytotoxicity in the presence and absence of light, cellular uptake, and intracellular fluorescence emission have been examined and are reported in this chapter. Chapter 6 describes a novel strategy to prepare low-symmetry phthalocyanines, which can serve as versatile platforms for the development of multi-functional phthalocyanine-based photosensitizers. By using an intracellular cyclization reaction of the pre-linked tetrakisphthalonitrile, the first ABCD-type zinc(II) phthalocyanine has been synthesized and characterized. By optimizing the reaction conditions, this compound can be prepared in 7.2 % yield. Chapter 7 concludes the present study while Chapter 8 reports the experimental details. All references mentioned in this thesis are provided in Chapter 9. 1H and 13C{1H} NMR spectra of all the new compounds are given in the Appendix. (Abstract shortened by ProQuest.).

Photodynamic evaluation of tetracarboxy-phthalocyanines in model systems.

PubMed

Alonso, Lais; Sampaio, Renato N; Souza, Thalita F M; Silva, Rodrigo C; Neto, Newton M Barbosa; Ribeiro, Anderson O; Alonso, Antonio; Gonçalves, Pablo J

2016-08-01

The present work reports the synthesis, photophysical and photochemical characterization and photodynamic evaluation of zinc, aluminum and metal free-base tetracarboxy-phthalocyanines (ZnPc, AlPc and FbPc, respectively). To evaluate the possible application of phthalocyanines as a potential photosensitizer the photophysical and photochemical characterization were performed using aqueous (phosphate-buffered solution, PBS) and organic (dimethyl sulfoxide, DMSO) solvents. The relative lipophilicity of the compounds was estimated by the octanol-water partition coefficient and the photodynamic activity evaluated through the photooxidation of a protein and photohemolysis. The photooxidation rate constants (k) were obtained and the hemolytic potential was evaluated by the maximum percentage of hemolysis achieved (Hmax) and the time (t50) to reach 50% of the Hmax. Although these phthalocyanines are all hydrophilic and possess very low affinity for membranes (log PO/W=-2.0), they led to significant photooxidation of bovine serum albumin (BSA) and photohemolysis. Our results show that ZnPc was the most efficient photosensitizer, followed by AlPc and FbPc; this order is the same as the order of the triplet and singlet oxygen quantum yields (ZnPc>AlPc>FbPc). Furthermore, together, the triplet, fluorescence and singlet oxygen quantum yields of zinc tetracarboxy-phthalocyanines suggest their potential for use in theranostic applications, which simultaneously combines photodiagnosis and phototherapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of non-peripherally tetra-5-methyl-1,3,4-thiadiazole substituted copper(II) iron(II) and oxo-titanium (IV) phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akyüz, Duygu; Akçay, Hakkı Türker; Barut, Burak; Koca, Atıf; Kantekin, Halit

2017-09-01

In this study novel substituted phthalonitrile (3) and non-peripherally tetra 5-Methyl-1,3,4-thiadiazole substituted copper(II) (4), iron(II) (5) and oxo-titanium (IV) (6) phthalocyanines were synthesized. These novel compounds were fully characterized by FT-IR, 1H NMR, UV-vis and MALDI-TOF mass spectroscopic techniques. Voltammetric and in situ spectroelectrochemical measurements were performed for metallo-phthalocyanines (4-6). TiIVOPc and FeIIPc showed metal-based and ligand-based electron transfer reactions while CuIIPc shows only ligand-based electron transfer reaction. Voltammetric measurements indicated that the complexes have reversible, diffusion controlled and one-electron redox reactions. The assignments of the redox processes and color of the electrogenerated species of the complexes were determined with in-situ spectroelectrochemical and electrocolorimetric measurements. These measurements showed that the complexes can be used as the electrochromic materials for various display technologies.

Assemblies of Boron Dipyrromethene/Porphyrin, Phthalocyanine, and C60 Moieties as Artificial Models of Photosynthesis: Synthesis, Supramolecular Interactions, and Photophysical Studies.

PubMed

Chen, Xiao-Fei; El-Khouly, Mohamed E; Ohkubo, Kei; Fukuzumi, Shunichi; Ng, Dennis K P

2018-03-12

A series of light-harvesting conjugates based on a zinc(II) phthalocyanine core with either two or four boron dipyrromethene (BODIPY) or porphyrin units have been synthesized and characterized. The conjugation of BODIPY/porphyrin units can extend the absorptions of the phthalocyanine core to cover most of the visible region. Upon addition of an imidazole-substituted C 60 (C 60 Im), it can axially bind to the zinc(II) center of the phthalocyanine core through metal-ligand interactions. The resulting complexes form photosynthetic antenna-reaction center mimics in which the BODIPY/porphyrin units serve as the antennas to capture the light and transfer the energy to the phthalocyanine core by efficient excitation energy transfer. The excited phthalocyanine is then quenched by the axially bound C 60 Im moiety by electron transfer, which has been supported by computational studies. The photoinduced processes of the assemblies have been studied in detail by various steady-state and time-resolved spectroscopic methods. By femtosecond transient absorption spectroscopic studies, the lifetimes of the charge-separated state of the bis(BODIPY) and bis(porphyrin) systems have been determined to be 3.2 and 4.0 ns, respectively. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A tightly coupled linear array of perylene, bis(porphyrin), and phthalocyanine units that functions as a photoinduced energy-transfer cascade

PubMed

Miller; Lammi; Prathapan; Holten; Lindsey

2000-10-06

We have prepared a linear array of chromophores consisting of a perylene input unit, a bis(free base porphyrin) transmission unit, and a free base phthalocyanine output unit for studies in artificial photosynthesis and molecular photonics. The synthesis involved four stages: (1) a rational synthesis of trans-AB2C-porphyrin building blocks each bearing one meso-unsubstituted position, (2) oxidative, meso,meso coupling of the zinc porphyrin monomers to afford a bis(zinc porphyrin) bearing one phthalonitrile group and one iodophenyl group, (3) preparation of a bis(porphyrin)-phthalocyanine array via a mixed cyclization involving the bis(free base porphyrin) and 4-tert-butylphthalonitrile, and (4) Pd-mediated coupling of an ethynylperylene to afford a perylene-bis(porphyrin)-phthalocyanine linear array. The perylene-bis(porphyrin)-phthalocyanine array absorbs strongly across the visible spectrum. Excitation at 490 nm, where the perylene absorbs preferentially, results in fluorescence almost exclusively from the phthalocyanine (phi(f) = 0.78). The excited phthalocyanine forms with time constants of 2 ps (90%) and 13 ps (10%). The observed time constants resemble those of corresponding phenylethyne-linked dyads, including a perylene-porphyrin (< or = 0.5 ps) and a porphyrin-phthalocyanine (1.1 ps (70%) and 8 ps (30%)). The perylene-bis(porphyrin)-phthalocyanine architecture exhibits efficient light-harvesting properties and rapid funneling of energy in a cascade from perylene to bis(porphyrin) to phthalocyanine.

Synthesis, aggregation and spectroscopic studies of novel water soluble metal free, zinc, copper and magnesium phthalocyanines and investigation of their anti-bacterial properties

NASA Astrophysics Data System (ADS)

Bayrak, Rıza; Akçay, Hakkı Türker; Beriş, Fatih Şaban; Şahin, Ertan; Bayrak, Hacer; Demirbaş, Ümit

2014-12-01

In this study, novel phthalonitrile derivative (3) was synthesized by the reaction between 4-nitrophthalonitrile (2) and a triazole derivative (1) containing pyridine moiety. Crystal structure of compound (3) was characterized by X-ray diffraction. New metal free and metallo-phthalocyanine complexes (Zn, Cu, and Mg) were synthesized using the phthalonitrile derivative (3). Cationic derivatives of these phthalocyanines (5, 7, 9, and 11) were prepared from the non-ionic phthalocyanines (4, 6, 8, and 10). All proposed structures were supported by instrumental methods. The aggregation behaviors of the phthalocyanines (4-11) were investigated in different solvents such as dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), chloroform and water. Water soluble cationic Pcs (5, 7, 9, and 11) aggregated in water and sodium dodecyl sulfate was used to prevent the aggregation. The second derivatives of the UV-Vis spectra of aggregated Pcs were used for analyzing the Q and B bands of aggregated species. Thermal behaviors of the phthalocyanines were also studied. In addition, anti-bacterial properties of the phthalocyanines were investigated. We used four gram negative and two gram positive bacteria to determine antibacterial activity of these compounds. Compound 7 has the best activity against the all bacteria with 125 μg/mL of MIC value. Compounds 4, 6, and 10 have the similar effect on the bacteria with 250 μg/mL of MIC value.

Nonperipheral Tetrakis(dibutylamino)phthalocyanines. New Types of 1,8,15,22-Tetrakis(substituted)phthalocyanine Isomers.

PubMed

Chen, Yuxiang; Fang, Wenjuan; Wang, Kang; Liu, Wei; Jiang, Jianzhuang

2016-09-19

Cyclic tetramerization of 3-(dibutylamino)phthalonitrile in refluxing n-pentanol in the presence of magnesium pentanoate afforded the four regioisomer-containing nonperipheral 1,8-/11,15-/18,22-/25-tetrakis(dibutylamino)phthalocyaninato magnesium complexes with the 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomer Mg{Pc[α-N(C4H9)2]4-C4} (2). This, in combination with its much superior crystallinity over the remaining three isomers, renders the easy isolation of 2 only through two simple recrystallizations from THF and methanol. Treatment of 2 with trifluoroacetic acid induced the isolation of metal-free 1,8,15,22-tetrakis(dibutylamino)phthalocyanine, H2{Pc[α-N(C4H9)2]4-C4} (1), which further reacted with M(OAc)2·nH2O (M = Ni, Zn) in refluxing n-pentanol, giving the 1,8,15,22-tetrakis(dibutylamino)phthalocyaninato metal complexes M{Pc[α-N(C4H9)2]4-C4} (M = Ni (3), Zn (4)). The full series of four 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric compounds have been characterized by a series of spectroscopic methods and single-crystal X-ray diffraction analyses. Obviously, the present result provides a simple and effective pathway for the synthesis and isolation of novel 1,8,15,22-tetrakis(dibutylamino)phthalocyanine isomeric derivatives, providing one step forward toward completing bis(alkyl)amino-incorporated phthalocyanine species.

Synthesis, aggregation and spectroscopic studies of novel water soluble metal free, zinc, copper and magnesium phthalocyanines and investigation of their anti-bacterial properties.

PubMed

Bayrak, Rıza; Akçay, Hakkı Türker; Beriş, Fatih Şaban; Sahin, Ertan; Bayrak, Hacer; Demirbaş, Ümit

2014-12-10

In this study, novel phthalonitrile derivative (3) was synthesized by the reaction between 4-nitrophthalonitrile (2) and a triazole derivative (1) containing pyridine moiety. Crystal structure of compound (3) was characterized by X-ray diffraction. New metal free and metallo-phthalocyanine complexes (Zn, Cu, and Mg) were synthesized using the phthalonitrile derivative (3). Cationic derivatives of these phthalocyanines (5, 7, 9, and 11) were prepared from the non-ionic phthalocyanines (4, 6, 8, and 10). All proposed structures were supported by instrumental methods. The aggregation behaviors of the phthalocyanines (4-11) were investigated in different solvents such as dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), chloroform and water. Water soluble cationic Pcs (5, 7, 9, and 11) aggregated in water and sodium dodecyl sulfate was used to prevent the aggregation. The second derivatives of the UV-Vis spectra of aggregated Pcs were used for analyzing the Q and B bands of aggregated species. Thermal behaviors of the phthalocyanines were also studied. In addition, anti-bacterial properties of the phthalocyanines were investigated. We used four gram negative and two gram positive bacteria to determine antibacterial activity of these compounds. Compound 7 has the best activity against the all bacteria with 125μg/mL of MIC value. Compounds 4, 6, and 10 have the similar effect on the bacteria with 250μg/mL of MIC value. Copyright © 2014 Elsevier B.V. All rights reserved.

Optical studies on phthalocyanines substituted with phenylazonaphthoxy groups

NASA Astrophysics Data System (ADS)

Özçeşmeci, İbrahim; Sorar, Idris; Gül, Ahmet

2016-10-01

The synthesis and characterization of peripherally ({1-[(Z or E)-phenylazo]-2-naphthyl} oxy) tetra-substituted metal-free and metallo (Zn(II), Co(II) and Cu(II)) phthalocyanines are described in this study. Aggregation properties of these compounds were investigated in the concentration range of 20-1 μM in tetrahydrofuran. Spectroscopic and photophysical properties of these phthalocyanines have been investigated in tetrahydrofuran. Thin films of metallophthalocyanines were prepared by spin coating technique. Results show that transmittance values of the films change with respect to the metal ions in the visible and Q absorptions regions. Films were also annealed at 100, 200 and 300 °C and their optical properties were investigated as a function of annealing temperature. The spectrophotometric measurements of transmittance spectra were carried out in the wavelength range 200-1000 nm. Results showed that transmittance values of ZnPc thin films were increased as a result of heat treatment.

Unprecedented chemosensing behavior of novel tetra-substituted benzimidazole zinc(II) phthalocynine for selective detection of Bi3 + ion: Synthesis, characterization and ROS generation

NASA Astrophysics Data System (ADS)

Ullah, Azeem; Shah, Faheem; Khan, Imran; Anwar, Muhammad; Shah, Kiramat; Muhammad, Munira Taj; Ahmad, Farid

2018-03-01

In this work, synthesis of novel symmetrical 4-(2-bromo-4-(5-bromo-1H-benzo[d] imidazol-2-yl) phenoxy) tetra substituted zinc phthalocyanine has been reported. The novel benzimidazole zinc phthlocynine compound (3) has been characterized by MALDI-TOF MS, FT-IR, UV-vis, and 1H NMR spectroscopy. This new compound 3 displayed excellent selectivity towards Bi3 + ion in the presence of other competitive ions including Ca2 +, Cd2 +, Co2 + Cu2 +, Fe3 +, Hg2 +, Sn2 +, Mg2 +, Na+, Ni2 + and Pb2 + respectively. Upon addition of Bi3 + into the solution of compound 3 in DMSO, dramatic change was observed in the Q- and the B-bands in UV-visible spectra as a result of donor acceptor interactions. Reactive oxygen species (ROS) were also studied using 2,7-dichlorofluorescin diacetate (DCFH-DA) a fluorescent probe which is converted to highly fluorescent dichlorofluorescein (DCF) in the presence of ROS. This property of non-aggregating zinc phthalocyanine is promising as a photosensitizer in photodynamic therapy of cancer.

Multinuclear Phthalocyanine-Fused Molecular Nanoarrays: Synthesis, Spectroscopy, and Semiconducting Property.

PubMed

Shang, Hong; Xue, Zheng; Wang, Kang; Liu, Huibiao; Jiang, Jianzhuang

2017-06-27

The post-cyclization strategy rather than the conventional ante-cyclotetramerization method was employed for the synthesis of multinuclear phthalocyanine-fused molecular nanoarrays. Reaction of 2,3,9,10,16,17-hexakis(2,6-dimethylphenoxy)-23,24-diaminophthalocyaninato zinc(II) with 2,7-di-tert-butylpyrene-4,5-dione, 2,7-di-tert-butylpyrene-4,5,9,10-tetraone, and hexaketocyclohexane in refluxing acetic acid afforded the corresponding mono-, bi-, and trinuclear phthalocyanine-fused zinc complexes (Pz-pyrene){Zn[Pc(OC 8 H 9 ) 6 ]} (1), (Pz 2 -pyrene){Zn[Pc(OC 8 H 9 ) 6 ]} 2 (2), {(HAT){Zn[Pc(OC 8 H 9 ) 6 ]} 3 } (3) in 46, 13, and 25 % yield, respectively, which extend the scope of multinuclear phthalocyanine-fused nanoarrays with different molecular skeletons. The self-assembly behavior of trinuclear phthalocyanine 3 in THF/CH 3 CN was investigated by electronic absorption spectroscopy and SEM, and the fabricated nanorods showed interesting semiconducting properties, which suggest good application potential of these multinuclear phthalocyanine-fused molecular nanoarrays. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amphiphilic zinc phthalocyanine photosensitizers: synthesis, photophysicochemical properties and in vitro studies for photodynamic therapy.

PubMed

Çakır, Dilek; Göksel, Meltem; Çakır, Volkan; Durmuş, Mahmut; Biyiklioglu, Zekeriya; Kantekin, Halit

2015-05-28

Peripherally and non-peripherally tetra-substituted zinc(ii) phthalocyanines bearing 2-(2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy)ethoxy and 2-(2-{2-[3-(diethylamino)phenoxy]ethoxy}ethoxy)ethoxy groups (, , and ) were synthesized by cyclotetramerization of the corresponding phthalonitriles (, , and ). Their quaternized ionic derivatives (, , and ) were also synthesized by the reaction of them with methyl iodide. The novel compounds were characterized by using standard spectroscopic techniques such as FT-IR, (1)H NMR, (13)C NMR, UV-vis, mass and elemental analyses. The obtained quaternized phthalocyanines (, , and ) showed amphiphilic behaviour with excellent solubility in both organic and aqueous solutions, which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel phthalocyanines were studied in DMSO for both non-ionic and ionic quaternized derivatives. However, these properties were examined in both DMSO and phosphate buffer solution (PBS) for quaternized ionic phthalocyanines. The effects of the positions of substituents (peripheral or non-peripheral) and the quaternization of the nitrogen atoms on the substituents about their photophysical and photochemical properties were also compared in this study. The bovine serum albumin (BSA) binding behaviours of the studied quaternized ionic zinc(ii) phthalocyanines were also described in PBS solutions. The quaternized phthalocyanines (, , and ) successfully displayed light-dependent photodamage in HeLa and HuH-7 cancer cells in photodynamic therapy treatment. The photosensitivity and the intensity of damage were found directly related to the concentration of the photosensitizers.

Synthesis of the iron phthalocyaninate radical cation μ-nitrido dimer and its interaction with hydrogen peroxide

NASA Astrophysics Data System (ADS)

Grishina, E. S.; Makarova, A. S.; Kudrik, E. V.; Makarov, S. V.; Koifman, O. I.

2016-03-01

The iron phthalocyaninate μ-nitrido dimer radical cation, as well as the μ-nitrido dimer complexes of iron phthalocyaninate, was found to have high catalytic activity in the oxidation of organic compounds. It was concluded that this compound is of interest as a model of active intermediates—catalase and oxidase enzymes.

Novel water soluble morpholine substituted Zn(II) phthalocyanine: Synthesis, characterization, DNA/BSA binding, DNA photocleavage and topoisomerase I inhibition.

PubMed

Barut, Burak; Demirbaş, Ümit; Özel, Arzu; Kantekin, Halit

2017-12-01

In this study, novel peripherally tetra 3-morpholinophenol substituted zinc(II) phthalocyanine (4) and its water soluble form quaternized zinc(II) phthalocyanine (ZnQ) were synthesized for the first time. These novel compounds were characterized by a combination of different spectroscopic techniques such as FT-IR, 1 H NMR, 13 C NMR, UV-vis and mass. The DNA binding of ZnQ was investigated using UV-vis absorption titration, competitive ethidium bromide, thermal denaturation and viscosity experiments that the ZnQ bound to CT-DNA via intercalation mode. ZnQ indicated photocleavage activity on supercoiled pBR322 plasmid DNA via formation of singlet oxygen under irradiation at 700nm. Besides, the topoisomerase I inhibitory effect experiments showed that ZnQ inhibited topoisomerase I enzyme in a concentration-dependent manner. The bovine serum albumin (BSA) binding experiments indicated that ZnQ bound to proteins through a static quenching mechanism. All of these results claim that ZnQ has potential agent for photodynamic therapy owing to its nucleic acid interactions and photobiological or photochemical properties. Copyright © 2017 Elsevier B.V. All rights reserved.

Lutetium(III) acetate phthalocyanines for photodynamic therapy applications: Synthesis and photophysicochemical properties.

PubMed

Mantareva, Vanya; Durmuş, Mahmut; Aliosman, Meliha; Stoineva, Ivanka; Angelov, Ivan

2016-06-01

The development of new water-soluble photosensitizers for photodynamic therapy (PDT) applications is a very active research topic. Efforts have been made to obtain the far-red absorbing phthalocyanine complexes with molecular design that facilitates the uptake and selectivity for a high PDT efficiency. The monomolecular lutetium(III) acetate phthalocyanines (LuPcs) substituted with methylpyridyloxy groups at non-peripheral (5) and peripheral (6) positions were synthesized by following the modification of the well-known synthetical routes. The photo-physicochemical properties of the both quaternized LuPcs were evaluated by the steady-state and time-resolved spectroscopy. The photochemical technique was applied to study the generation of the singlet oxygen. Two water-soluble and cationic LuPcs were synthesized and chemically characterized. The photo-physicochemical properties of absorption (675 and 685nm) and the red shifted fluorescence (704 and 721nm) as well as the fluorescence lifetimes (2.24 and 3.27ns) were studied. The promising values of singlet oxygen quantum yields (0.32 for 5 and 0.35 for 6) were determined. Lutetium(III) acetate phthalocyanine complexes were synthesized and evaluated with physicochemical properties suitable for future photodynamic therapy applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Metal Phthalocyanine Sheet Polymers

NASA Technical Reports Server (NTRS)

Achar, B. N.; Fohlen, G. M.; Parker, J. A.

1986-01-01

New method for synthesizing metal phthalocyanine tetracarboxylic acids (MPTCA's) yields high purity end product. In addition, high-purity metal phthalocyanine sheet polymers synthesized from compounds. Monomer formed into sheet polymer by heating. Units of polymer linked in manner similar to phenyl-group linkages in biphenyl: Conjugation extends throughout macromolecule, thereby increasing delocalization of TT-electrons. Increases conductivity and thermal stability of polymer.

Zinc phthalocyanines attached to gold nanorods for simultaneous hyperthermic and photodynamic therapies against melanoma in vitro.

PubMed

Freitas, L F; Hamblin, M R; Anzengruber, F; Perussi, J R; Ribeiro, A O; Martins, V C A; Plepis, A M G

2017-08-01

Studies indicate that hyperthermic therapy using gold nanorods and photodynamic activity with many photosensitizers can present a synergistic effect, and offer a great therapeutic potential, although more investigation needs to be performed before such approach could be implemented. We proposed to investigate the effect of the attachment of phthalocyanines on the surface of gold nanorods (well-characterized devices for hyperthermia generation) for the elimination of melanoma, one of the most important skin cancers due to its high lethality. Following the synthesis of nanorods through a seed-mediated method, the efficacy of photodynamic therapy (PDT) and hyperthermia was assessed separately. We chose to coat the nanorods with two tetracarboxylated zinc phthalocyanines - with or without methyl-glucamine groups. After the coating process, the phthalocyanines formed ionic complexes with the cetyltrimethylammonium bromide (CTAB) that was previously covering the nanoparticles. The nanorod-phthalocyanines complexes were analyzed by transmission electron microscopy (TEM), and their singlet oxygen and hydroxyl radical generation yields were assessed. Furthermore, they were tested in vitro with melanotic B16F10 and amelanotic B16G4F melanoma cells. The cells with nanoparticles were irradiated with laser (at 635nm), and the cell viability was assessed. The results indicate that the photodynamic properties of the phthalocyanines tested are enhanced when they are attached on the nanorods surface, and the combination of PDT and hyperthermia was able to eliminate over 90% of melanoma cells. This is a novel study because two tetracarboxylated phthalocyanines were used and because the same wavelength was irradiated to activate both the nanorods and the photosensitizers. Copyright © 2017 Elsevier B.V. All rights reserved.

Phthalocyanine Tetraamine Epoxy-Curing Agents

NASA Technical Reports Server (NTRS)

Fohlen, G. M.; Achar, B. N.; Parker, J. A.

1986-01-01

Tough fire- and chemical-resistant epoxies produced by using metalphthalocyanine tetraamines (MPT's) of copper, cobalt, or nickel as curing agents. Synthesis of MPT's commercially realizable and gives pure compounds with almost 90-percent yield. Synthesis applicable for metals with atomic radii of about 1.35 angstroms, including Cu, Co, Ni, Zn, Fe, Pt, Al, and V. Possible to use metal phthalocyanines to cure epoxy resins in homogeneous reaction.

Simultaneous determination of theophylline and caffeine on novel [Tetra-(5-chloroquinolin-8-yloxy) phthalocyanato] manganese(III)-Carbon nanotubes composite electrode.

PubMed

Koçak, Çağrı Ceylan; Nas, Asiye; Kantekin, Halit; Dursun, Zekerya

2018-07-01

This work reports the synthesis of new symmetrically substituted manganese(III) phthalocyanine (2eOHMnPc) (2) containing tetra 5-chloroquinolin-8-yloxy group at the peripheral position for the first time. Manganese(III) phthalocyanine (2) was synthesized by cyclotetramerization of 4-(5-chloroquinolin-8-yloxy)phthalonitrile (1) in the presence of corresponding metal salt (manganese(II) chloride). This peripherally substituted phthalocyanine complex (2) was purified by column chromatography and characterized by several techniques such as IR, mass and UV-Visible spectral data. This novel synthesized phthalocyanine was mixed with multiwalled carbon nanotubes in order to prepare the novel catalytic surface on glassy carbon electrode for theophylline and caffeine detection in acidic medium. The novel composite electrode surfaces were characterized by scanning electron microscopy and electrochemical impedance spectroscopy. Individual and simultaneous determination of theophylline and caffeine were studied by differential pulse voltammetry. The detection limits were individually calculated for theophylline and caffeine as 6.6 × 10 -9 M and 5.0 × 10 -8 M, respectively. In simultaneous determination, LODs were calculated for theophylline and caffeine as 8.1 × 10 -9 M and 3.0 × 10 -7 M, respectively. The practical applicability of the proposed modified electrode was tested for the determination of theophylline and caffeine in green tea, cola and theophylline serum. Copyright © 2018 Elsevier B.V. All rights reserved.

Functionalization of multi-walled carbon nanotubes with iron phthalocyanine via a liquid chemical reaction for oxygen reduction in alkaline media

NASA Astrophysics Data System (ADS)

Yan, Xiaomei; Xu, Xiao; Liu, Qin; Guo, Jia; Kang, Longtian; Yao, Jiannian

2018-06-01

Iron single-atom catalyst in form of iron-nitrogen-carbon structure possesses the excellent catalytic activity in various chemical reactions. However, exploring a sustainable and stable single-atom metal catalyst still faces a great challenge due to low yield and complicated synthesis. Here, we report a functional multi-wall carbon nanotubes modified with iron phthalocyanine molecules via a liquid chemical reaction and realize the performance of similar single-atom catalysis for oxygen reduction reaction. A serial of characterizations strongly imply the structure change of iron phthalocyanine molecule and its close recombination with multi-wall carbon nanotubes, which are in favor of ORR catalysis. Compared to commercial platinum-carbon catalyst, composites exhibit superior activity for oxygen reduction reaction with higher half-wave potential (0.86 V), lower Tafel slope (38 mV dec-1), higher limiting current density and excellent electrochemical stability. The corresponding Zinc-air battery also presents higher maximum power density and discharge stability. Therefore, these findings provide a facile route to synthesize a highly efficient non-precious metal carbon-based catalyst.

Phthalocyanine-sulfonamide conjugates: Synthesis and photodynamic inactivation of Gram-negative and Gram-positive bacteria.

PubMed

da Silva, Raquel Nunes; Cunha, Ângela; Tomé, Augusto C

2018-06-25

Phthalocyanines bearing four or eight sulfonamide units were synthesized and their efficiency in the photodynamic inactivation of Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria was evaluated. Conjugates with simpler sulfonamide units (N,N-diethylbenzenesulfonamide, N-isopropylbenzenesulfonamide and N-(4-methoxyphenyl)benzenesulfonamide) caused stronger inactivation than those with heterocyclic groups (N-(thiazol-2-yl)benzenesulfonamide) or long alkyl chains (N-dodecylbenzenesulfonamide) in both bacteria. Furthermore, the encapsulation of the phthalocyanine-sulfonamide conjugates within polyvinylpyrrolidone micelles, used as drug delivery vehicles, in general showed to enhance the inactivation efficiency. The results show that encapsulated phthalocyanine-sulfonamide conjugates are a promising class of photosensitizers to be used in photodynamic antimicrobial therapy. Copyright © 2018 Elsevier Masson SAS. All rights reserved.

Synthesis, structures, and properties of crystalline salts with radical anions of metal-containing and metal-free phthalocyanines.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Faraonov, Maxim A; Ishikawa, Manabu; Khasanov, Salavat S; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2015-01-12

Radical anion salts of metal-containing and metal-free phthalocyanines [MPc(3-)](·-), where M = Cu(II), Ni(II), H2, Sn(II), Pb(II), Ti(IV)O, and V(IV)O (1-10) with tetraalkylammonium cations have been obtained as single crystals by phthalocyanine reduction with sodium fluorenone ketyl. Their formation is accompanied by the Pc ligand reduction and affects the molecular structure of metal phthalocyanine radical anions as well as their optical and magnetic properties. Radical anions are characterized by the alternation of short and long C-Nimine bonds in the Pc ligand owing to the disruption of its aromaticity. Salts 1-10 show new bands at 833-1041 nm in the NIR range, whereas the Q- and Soret bands are blue-shifted by 0.13-0.25 eV (38-92 nm) and 0.04-0.07 eV (4-13 nm), respectively. Radical anions with Ni(II), Sn(II), Pb(II), and Ti(IV)O have S = 1/2 spin state, whereas [Cu(II)Pc(3-)](·-) and [V(IV)OPc(3-)](·-) containing paramagnetic Cu(II) and V(IV)O have two S = 1/2 spins per radical anion. Central metal atoms strongly affect EPR spectra of phthalocyanine radical anions. Instead of narrow EPR signals characteristic of metal-free phthalocyanine radical anions [H2Pc(3-)](·-) (linewidth of 0.08-0.24 mT), broad EPR signals are manifested (linewidth of 2-70 mT) with g-factors and linewidths that are strongly temperature-dependent. Salt 11 containing the [Na(I)Pc(2-)](-) anions as well as previously studied [Fe(I)Pc(2-)](-) and [Co(I)Pc(2-)](-) anions that are formed without reduction of the Pc ligand do not show changes in molecular structure or optical and magnetic properties characteristic of [MPc(3-)](·-) in 1-10. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Large-scale synthesis of high-purity well-aligned carbon nanotubes using pyrolysis of iron(II) phthalocyanine and acetylene

NASA Astrophysics Data System (ADS)

Liu, B. C.; Lee, T. J.; Lee, S. H.; Park, C. Y.; Lee, C. J.

2003-08-01

Well-aligned carbon nanotubes (CNTs) with high purity have been produced by pyrolysis of iron(II) phthalocyanine and acetylene at 800 °C. The synthesized CNTs have a length of 75 μm and diameters ranging from 20 to 60 nm. The CNTs have a bamboo-like structure and exhibit good crystallinity of graphite sheets. The growth rate of the CNTs was rapidly increased with adding C 2H 2. Our results demonstrate that the proposed growth method is suitable to large-scale synthesis of high-purity well-aligned CNTs on various substrates.

Non-aggregated axially disubstituted silicon phthalocyanines bearing electropolymerizable ligands and their aggregation, electropolymerizaton and thermal properties.

PubMed

Biyiklioglu, Zekeriya; Bas, Huseyin; Alp, Hakan

2015-08-21

A novel series of axially disubstituted silicon(iv) phthalocyanines bearing electropolymerizable ligands were designed and synthesized for the first time. The silicon(iv) phthalocyanines were characterized by various spectroscopic techniques as well as elemental analysis. The aggregation behavior of the SiPcs were examined in different solvents and at different concentrations in chloroform. In all the studied solvents and concentrations, the SiPcs were non-aggregated. The thermal behavior of the silicon(iv) phthalocyanines was also studied. The electropolymerization properties of the silicon(iv) phthalocyanines were investigated by cyclic and square wave voltammetry. This study is the first example of the electropolymerization of axially disubstituted silicon phthalocyanines. The type of axial ligand on the phthalocyanine ring did not show any effect on the absorption and thermal properties but influenced the electropolymerization of the phthalocyanines.

Synthesis of size controllable cu-phthalocyanine nanofibers by simple solvent diffusion method and their electrochemical properties.

PubMed

Gao, Junshan; Cheng, Chuanwei; Zhou, Xuechao; Li, Yingying; Xu, Xiaoqi; Du, Xiguang; Zhang, Haiqian

2010-02-15

Tetra (2-isopropyl-5-methylphenoxy) substituted Cu-phthalocyanine nanofibers were obtained in large scale by a simple solvent diffusion method. The sizes of the fibers can be finely tuned under different solvent temperature. FE-SEM micrographs indicate that the length of the fibers changed from several hundreds micrometers to several hundreds nanometers and the width changed from several micrometers to several decade nanometers. XRD measurement showed a highly long-range ordered lamellar arrangement of the substituted Cu-phthalocyanine molecules in the microfiber and the UV-vis absorption spectrum of the fibers indicated an H-aggregate of the phthalocyanine molecules. The CV curves elucidate the CuPc fibers can be fabricated Faraday pseudocapacitor. Crown Copyright 2009. Published by Elsevier Inc. All rights reserved.

Fabrication and characterization of inverted organic solar cells using shuttle cock-type metal phthalocyanine and PCBM:P3HT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Furukawa, Ryo, E-mail: suzuki@mat.usp.ac.jp; Akiyama, Tsuyoshi, E-mail: suzuki@mat.usp.ac.jp

2015-02-27

Inverted organic solar cells using shuttle cock-type phthalocyanine, semiconducting polymer and fullerenes were fabricated and characterized. Photovoltaic and optical properties of the solar cells with inverted structures were investigated by optical absorption, current density-voltage characteristics. The photovoltaic properties of the tandem organic solar cell using titanyl phthalocyanine, vanadyl phthalocyanine, poly(3-hexylthiophene) (P3HT) and [6, 6]-phenyl C{sub 61}-butyric acid methyl ester (PCBM) were improved. Effect of annealing and solvent treatment on surface morphologies of the active layer was investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed for improvement of the photovoltaic performance.

Photochemical and Photophysical Properties of Phthalocyanines Modified with Optically Active Alcohols.

PubMed

Ramos, Aline A; Nascimento, Francisco B; de Souza, Thaiza F M; Omori, Alvaro T; Manieri, Tânia M; Cerchiaro, Giselle; Ribeiro, Anderson O

2015-07-24

Three phthalocyanine derivatives were synthesized and characterized: one modified with a racemic mixture of 1-(4-bromophenyl)ethanol and two other macrocycles modified with each one of the enantioenriched isomers (R)-1-(4-bromophenyl)ethanol and (S)-1-(4-bromophenyl)ethanol. The compounds were characterized by 1H-NMR spectroscopy, mass spectrometry, UV-Vis absorption, and excitation and emission spectra. Additionally, partition coefficient values and the quantum yield of the generation of oxygen reactive species were determined. Interestingly, the phthalocyanine containing a (R)-1-(4-bromophenyl)ethoxy moiety showed higher quantum yield of reactive oxygen species generation than other compounds under the same conditions. In addition, the obtained fluorescence microscopy and cell viability results have shown that these phthalocyanines have different interactions with mammary MCF-7 cells. Therefore, our results indicate that the photochemical and biological properties of phthalocyanines with chiral ligands should be evaluated separately for each enantiomeric species.

Microwave-Mediated Synthesis of Bulky Lanthanide Porphyrin-Phthalocyanine Triple-Deckers: Electrochemical and Magnetic Properties.

PubMed

Jin, Hong-Guang; Jiang, Xiaoqin; Kühne, Irina A; Clair, Sylvain; Monnier, Valérie; Chendo, Christophe; Novitchi, Ghenadie; Powell, Annie K; Kadish, Karl M; Balaban, Teodor Silviu

2017-05-01

Five heteroleptic lanthanide porphyrin-bis-phthalocyanine triple-decker complexes with bulky peripheral groups were prepared via microwave-assisted synthesis and characterized in terms of their spectroscopic, electrochemical, and magnetic properties. These compounds, which were easily obtained under our preparative conditions, would normally not be accessible in large quantities using conventional synthetic methods, as a result of the low yield resulting from steric congestion of bulky groups on the periphery of the phthalocyanine and porphyrin ligands. The electrochemically investigated triple-decker derivatives undergo four reversible one-electron oxidations and three reversible one-electron reductions. The sites of oxidation and reduction were assigned on the basis of redox potentials and UV-vis spectral changes during electron-transfer processes monitored by thin-layer spectroelectrochemistry, in conjunction with assignments of electronic absorption bands of the neutral compounds. Magnetic susceptibility measurements on two derivatives containing Tb III and Dy III metal ions reveal the presence of ferromagnetic interactions, probably resulting from magnetic dipolar interactions. The Tb III derivative shows SMM behavior under an applied field of 0.1 T, where the direct and Orbach process can be determined, resulting in an energy barrier of U eff = 132.0 K. However, Cole-Cole plots reveal the presence of two relaxation processes, the second of which takes place at higher frequencies, with the data conforming to a 1/t ∝ T 7 relation, thus suggesting that it can be assigned to a Raman process. Attempts were made to form two-dimensional (2D) self-assembled networks on a highly oriented pyrolytic graphite (HOPG) surface but were unsuccessful due to bulky peripheral groups on the two Pc macrocycles.

Characterization of phthalocyanine functionalized quantum dots by dynamic light scattering, laser Doppler, and capillary electrophoresis.

PubMed

Ramírez-García, Gonzalo; Oluwole, David O; Nxele, Siphesihle Robin; d'Orlyé, Fanny; Nyokong, Tebello; Bedioui, Fethi; Varenne, Anne

2017-02-01

In this work, we characterized different phtalocyanine-capped core/shell/shell quantum dots (QDs) in terms of stability, ζ-potential, and size at various pH and ionic strengths, by means of capillary electrophoresis (CE), and compared these results to the ones obtained by laser Doppler electrophoresis (LDE) and dynamic light scattering (DLS). The effect of the phthalocyanine metallic center (Zn, Al, or In), the number (one or four), and nature of substituents (carboxyphenoxy- or sulfonated-) of functionalization on the phthalocyanine physicochemical properties were evaluated. Whereas QDs capped with zinc mono-carboxyphenoxy-phtalocyanine (ZnMCPPc-QDs) remained aggregated in the whole analyzed pH range, even at low ionic strength, QDs capped with zinc tetracarboxyphenoxy phtalocyanine (ZnTPPc-QDs) were easily dispersed in buffers at pH equal to or higher than 7.4. QDs capped with aluminum tetrasulfonated phthalocyanine (AlTSPPc-QDs) and indium tetracarboxyphenoxy phthalocyanines (InTCPPc-QDs) were stable in aqueous suspension only at pH higher than 9.0 due to the presence of functional groups bound to the metallic center of the phthalocyanine. The ζ-potential values determined by CE for all the samples decreased when ionic strength increased, being well correlated with the aggregation of the nanoconjugates at elevated salt concentrations. The use of electrokinetic methodologies has provided insights into the colloidal stability of the photosensitizer-functionalized QDs in physiological relevant solutions and thereby, its usefulness for improving their design and applications for photodynamic therapy. Graphical Abstract Schematic illustration of the phthalocyanine capped QDs nanoconjugates and the capillary electrophoresis methods applied for size and ζ-potential characterization.

Synthesis and Electric Properties of a Two-Dimensional Metal-Organic Framework Based on Phthalocyanine.

PubMed

Nagatomi, Hisanori; Yanai, Nobuhiro; Yamada, Teppei; Shiraishi, Kanji; Kimizuka, Nobuo

2018-02-06

Complexation of copper(II) 2,3,9,10,16,17,23,24-octahydroxy-29H,31H-phthalocyanine (CuPcOH) with copper(II) ions gives a two-dimensional (2D) metal-organic framework (MOF). This is the first report of a phthalocyanine-based MOF. This 2D MOF was obtained as a black powder and showed an electrical conductivity of 1.6×10 -6  S cm -1 at 80 °C. When this MOF is used as a cathode of lithium ion battery (LIB), large charge/discharge capacities of 151/128 mAh g -1 were obtained. In addition, it showed a good stability during 200 charge/discharge cycles. The obtained LIB performance mainly originates from the electrically conductive and redox-active framework of the phthalocyanine-based 2D MOF and its hierarchical microporous/mesoporous structure. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of proton transfer from tetra(4-nitro-5- tert-butyl)phthalocyanine to nitrogen-containing bases in benzene

NASA Astrophysics Data System (ADS)

Petrov, O. A.; Kuzmina, E. L.; Maizlish, V. E.; Rodionov, A. V.

2014-01-01

The acid-basic interaction between tetra(4-nitro-5- tert-butyl)phthalocyanine and pyridine, 2-methylpyridine, morpholine, piperidine, n-butylamine, diethylamine, and triethylamine in benzene is studied. It is found that the intermolecular transfer of protons of NH groups from tetra(4-nitro-5- tert-butyl)phthalocyanine to morpholine and diethylamine is characterized by unusually low values of the reaction constant rates. The effect of the structure of tetra(4-nitro-5- tert-butyl)phthalocyanine and tetra(3-nitro-5- tert-butyl)phthalocyanine, and of the nature of the base on the kinetic parameters of acid-base interaction is demonstrated. A structure is proposed for complexes with the transfer of displaced phthalocyanines' protons. It is found that they undergo decomposition over time.

Novel non-symmetrical bifunctionally-substituted phthalonitriles and corresponding d-metal phthalocyaninates

NASA Astrophysics Data System (ADS)

Vashurin, Artur; Maizlish, Vladimir; Tikhomirova, Tatiyana; Nemtseva, Marina; Znoyko, Serafima; Aleksandriiskii, Viktor

2018-05-01

The work reports synthesis of 4-(2-tert-butyl-4,5-dicyanophenylsulfonyl)benzene and its analogue containing carboxyl group in phenyl fragment by nucleophilic substitution of nitro-group of 4-tert-butyl-5-nitrophthalonitrile. Unique structure of the obtained compounds is explained by presence of bulky tert-butyl substituent in combination with carboxyl group, which being part of phthalocyanine molecule impart it higher solubility within different solvents (organic and water mediums) and act as anchoring groups. Based on obtained nitriles phthalocyanine complexes of copper, nickel, cobalt and magnesium are synthesized with good yields. Demetallization of initial magnesium phthalocyanine by hydrochloric acid was performed in order to obtain ligand of phthalocyanine. Synthetic and purification techniques are described in detail. Obtained substances are of specific structure making them to be applied in sensorics for smart materials production, as sensitizers or part of molecular magnets. The structure, NMR and IR spectra are modeled using special software. Resulting experimental and theoretical data are compared. The results show sufficient correlation that confirms correctness of chosen methods and its applicability for theoretical studying compounds related to investigated ones.

Photochemistry of transition-metal phthalocyanines. Mechanistic aspects of the photochemistry of the acido(phthalocyanine)rhodium(III) complexes investigated by continuous, flash, and laser flash photolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muralidharan, S.; Ferraudi, G.; Schmatz, K.

1982-08-01

Rh(ph)(CH/sub 3/OH)X, X = Cl, Br, or I, has been prepared and characterized. Continuous-wave irradiations of these phthalocyanines in the ultraviolet region of the spectrum, in acetonitrile and acetonitrile-isopropyl alcohol mixtures, result in the redox-induced substitution of the axially coordinated halide ions by the solvent. Even though the overall reaction was photosubstitution, the intermediates observed by conventional and laser flash photolysis were found to be rhodium(II) phthalocyanine and rhodium(III) phthalocyanine ligand radicals. The photoredox processes were attributed to the population of (n..pi..*) ligand-centered excited states that involve the lone electron pair from the bridge nitrogens of the phthalocyanine ligand. 9more » figures, 3 tables.« less

Photophysical characterization of a cytidine-guanosine tethered phthalocyanine-fullerene dyad.

PubMed

Torres, Tomas; Gouloumis, Andreas; Sanchez-Garcia, David; Jayawickramarajah, Janarthanan; Seitz, Wolfgang; Guldi, Dirk M; Sessler, Jonathan L

2007-01-21

A new non-covalent electron transfer model system, based on the use of cytidine-guanosine hydrogen bonding interactions, is described that incorporates a phthalocyanine photodonor and a C60 fullerene acceptor.

Multi-modular, tris(triphenylamine) zinc porphyrin-zinc phthalocyanine-fullerene conjugate as a broadband capturing, charge stabilizing, photosynthetic 'antenna-reaction center' mimic.

PubMed

Kc, Chandra B; Lim, Gary N; D'Souza, Francis

2015-04-21

A broadband capturing, charge stabilizing, photosynthetic antenna-reaction center model compound has been newly synthesized and characterized. The model compound is comprised of a zinc porphyrin covalently linked to three units of triphenylamine entities and a zinc phthalocyanine entity. The absorption and fluorescence spectra of zinc porphyrin complemented that of zinc phthalocyanine offering broadband coverage. Stepwise energy transfer from singlet excited triphenylamine to zinc porphyrin, and singlet excited zinc porphyrin to zinc phthalocyanine (kENT ∼ 10(11) s(-1)) was established from spectroscopic and time-resolved transient absorption techniques. Next, an electron acceptor, fullerene was introduced via metal-ligand axial coordination to both zinc porphyrin and zinc phthalocyanine centers, and they were characterized by spectroscopic and electrochemical techniques. An association constant of 4.9 × 10(4) M(-1) for phenylimidazole functionalized fullerene binding to zinc porphyrin, and 5.1 × 10(4) M(-1) for it binding to zinc phthalocyanine was obtained. An energy level diagram for the occurrence of different photochemical events within the multi-modular donor-acceptor conjugate was established from spectral and electrochemical data. Unlike the previous zinc porphyrin-zinc phthalocyanine-fullerene conjugates, the newly assembled donor-acceptor conjugate has been shown to undergo the much anticipated initial charge separation from singlet excited zinc porphyrin to the coordinated fullerene followed by a hole shift process to zinc phthalocyanine resulting in a long-lived charge separated state as revealed by femto- and nanosecond transient absorption spectroscopic techniques. The lifetime of the final charge separated state was about 100 ns.

[Spectrum characterization and fine structure of copper phthalocyanine-doped TiO2 microcavities].

PubMed

Liu, Cheng-lin; Zhang, Xin-yi; Zhong, Ju-hua; Zhu, Yi-hua; He, Bo; Wei, Shi-qiang

2007-10-01

Copper phthalocyanine-doped TiO2 microcavities were fabricated by chemistry method. Their spectrum characterization was studied by Fourier transform infrared (FTIR) and Raman spectroscopy, and their fine structure was analyzed by X-ray absorption fine structure (XAFS). The results show that there is interaction of copper phthalocyanine (CuPc) and TiO2 microcavities after TiO2 microcavities was doped with CuPc. For example, there is absorption at 900.76 cm(-1) in FTIR spectra, and the "red shift" of both OH vibration at 3392.75 cm(-1) and CH vibration at 2848.83 cm(-1). There exist definite peak shifts and intensity changes in infrared absorption in the C-C or C-N vibration in the planar phthalocyanine ring, the winding vibration of C-H inside and C-N outside plane of benzene ring. In Raman spectrum, there are 403.4, 592.1 and 679.1 cm(-1) characterized peaks of TiO2 in CuPc-doped TiO2 microcavities, but their wave-numbers show shifts to anatase TiO2. The vibration peaks at 1586.8 and 1525.6 cm(-1) show that there exists the composite material of CuPc and TiO2. These changes are related to the plane tropism of the molecule structure of copper phthalocyanine. XAFS showed tetrahedron TiO4 structure of Ti in TiO2 microcavities doped with copper phthalocyanine, and the changes of inner "medial distances" and the surface structure of TiO2 microcavities.

Electropolymerizable peripherally tetra-{2-[3-(diethylamino)phenoxy]ethoxy} substituted as well as axially (4-phenylpiperazin-1-yl)propanoxy-disubstituted silicon phthalocyanines and their electrochemistry.

PubMed

Biyiklioglu, Zekeriya; Alp, Hakan

2015-11-21

A novel type of peripherally tetra-substituted as well as axially disubstituted silicon(iv) phthalocyanine containing electropolymerizable ligands was designed and synthesized for the first time. Axial bis-hydroxy silicon phthalocyanine 2 was prepared from 2(3),9(10),16(17),23(24)-tetrakis-{2-[3-(diethylamino)phenoxy]ethoxy}phthalocyanine 1 in dichloromethane by using 1.8-diazabicyclo[5.4.0]undec-7-ene (DBU) and trichlorosilane. Peripherally tetra and axially di-substituted silicon phthalocyanine 4 was synthesized from 2(3),9(10),16(17),23(24)-tetrakis-{2-[3-(diethylamino)phenoxy]ethoxy}silicon(iv)phthalocyanine dihydroxide 2 with 1-(3-chloropropyl)-4-phenylpiperazine 3 in toluene in the presence of NaH at 120 °C. These complexes were fully characterized by various spectroscopy techniques such as (1)H-NMR, (13)C-NMR, IR, UV-Vis, and MALDI-TOF spectroscopy and elemental analysis as well. Electropolymerization properties of silicon(IV) phthalocyanine complexes were investigated by cyclic and square wave voltammetry. Electrochemical studies reveal that silicon(IV) phthalocyanine complexes were electropolymerized on the working electrode during the anodic potential scan. This study is the first example of electropolymerization of both peripherally tetra and axially di-substituted silicon phthalocyanines on the same molecule.

Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor.

PubMed

Sánchez-De la Torre, Fernando; De la Rosa, Javier Rivera; Kharisov, Boris I; Lucio-Ortiz, Carlos J

2013-09-30

Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), and N₂ physisorption isotherms were also determined. The Ni/Al₂O₃ sample reveled agglomerated (1 μm) of nanoparticles of Ni (30-80 nm) however, NiO particles were also identified, probably for the low temperature during the H 2 reduction treatment (350 °C), the Cu/Al₂O₃ sample presented agglomerates (1-1.5 μm) of nanoparticles (70-150 nm), but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH₃ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption.

Characterization and degradation studies on synthetic polymers for aerospace application

NASA Technical Reports Server (NTRS)

Hsu, M. T. S.

1982-01-01

The anti-misting additive for jet fuels known as FM-9 (proprietary polymer) was characterized by elemental analysis, solubility studies and molecular weight determination. Physical properties of surface tension, viscosity, specific gravity and other physical parameters were determined. These results are compared with properties of polyisobutylene and fuels modified with the same; the misting characteristics of polyisobutylene and FM-9 in Jet A fuel are included. Characterization and degradation of phthalocyanine and its derivatives were accomplished by use of a mass spectrometer and a pyroprobe solid pyrolyzer. Metal phthalocyanine tetracarboxylic acids and phthalocyanine-tetraamine cured epoxies were studied. Epoxy/graphite composite panels were exposed to a NASA-Ames radiant panel fire simulator in the flaming and non-flaming modes; toxic gases of HCN and HZS were measured along with oxygen, Co2, Co, and organic gases.

Solventless and One-Pot Synthesis of Cu(II) Phthalocyanine Complex: A Green Chemistry Experiment

ERIC Educational Resources Information Center

Sharma, R. K.; Sharma, Chetna; Sidhwani, Indu Tucker

2011-01-01

With the growing awareness of green chemistry, it is increasingly important for students to understand this concept in the context of laboratory experiments. Although microwave-assisted organic synthesis has become a common and invaluable technique in recent years, there have been few procedures published for microwave-assisted inorganic synthesis…

Investigation of the photophysical and photochemical properties of peripherally tetra-substituted water-soluble zwitterionic and cationic zinc(ii) phthalocyanines.

PubMed

Çolak, Senem; Durmuş, Mahmut; Yıldız, Salih Zeki

2016-06-21

In this study, 4-{4-[N-((3-dimethylamino)propyl)amide]phenoxy}phthalonitrile () and its zinc(ii) phthalocyanine derivative () were synthesized for the first time. 4-(N-((3-Dimethylamino)propyl)amide)phenoxy substituted zinc(ii) phthalocyanine () was converted to its water-soluble sulfobetaine (), betaine () and N-oxide () containing zwitterionic and quaternized cationic () derivatives. All newly synthesized compounds () were characterized by the combination of UV-vis, FT-IR, (1)H NMR, mass spectroscopy techniques and elemental analysis. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen quantum yields) properties were investigated in DMSO for all the synthesized zinc(ii) phthalocyanines () and in both DMSO and aqueous solutions for zwitterionic and cationic phthalocyanines () for the specification of their capability as photosensitizers in photodynamic therapy (PDT). The binding behavior of water soluble phthalocyanines () to the bovine serum albumin protein was also examined for the determination of their transportation ability in the blood stream.

Photophysical properties of a novel axially substituted tetra-α-(pentyloxy) Titanium(IV) Phthalocyanine - Hematoxylin

NASA Astrophysics Data System (ADS)

Jiang, Yufeng; Lv, Huafei; Yu, Xinxin; Pan, Sujuan; Zhang, Tiantian; Huang, Yide; Wang, Yuhua; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2017-06-01

Metal phthalocyanines (MPcs) are a very important class of widespread application compounds. They are not only used as dyes but also used as catalysts, data storage, electron charge carriers in photocopiers, photoconductors in chemical sensors, and photo-antenna devices in photosysthesis, photovoltaic cells. A particular application of Pcs is that it was used as a photosensitizers (PS) for treatment of certain cancer by photodynamic therapy of cancer and non-cancer diseases. However, the molecular aggregation of phthalocyanines, which is an intrinsic property of these large π-π conjugated systems, provides an efficient non-radioactive energy relaxation pathway, thereby shortening the excited state lifetimes, and reducing the photosensitizing and target efficiency. To overcome these problems, the introduction of axial ligands to phthalocyanine can prevent the formation of aggregation to some extend. In this paper, hematoxylin axially substituted tetra-α-(pentoxy) titanium (IV) phthalocyanine (TiPc(OC5H11)4-Hematoxylin) were characterized by elemental analysis, IR, 1H NMR, UV-Vis, fluorescence spectra. No obviously Q band change was observed after the hematoxylin was substituted at the peripheral position of substituted phthalocyanine ring. Because of the rigidity structure of the hematoxylin, the fluorescence intensity of hematoxylin peripheral substituted phthalocyanine decreased compared with free substituted phthalocyanines. The fluorescence lifetimes of axially substituted phthalocyanine was fitted to be 3.613 ns. This compound may be considered as a promising photosensitizer for PDT.

Electrochemical and optical characterization of cobalt, copper and zinc phthalocyanine complexes.

PubMed

Lee, Jaehyun; Kim, Se Hun; Lee, Woosung; Lee, Jiwon; An, Byeong-Kwan; Oh, Se Young; Kim, Jae Pil; Park, Jongwook

2013-06-01

New phthalocyanine (Pc) derivatives that include the alkyl group in ligand were synthesized based on three core metals such as zinc (Zn), copper (Cu), and cobalt (Co). Electrochemical behaviors and optical properties of the new phthalocyanine derivatives with ligand and different core metal were investigated by using cyclic voltammetry, UV-Visible (UV-Vis) spectroscopy and photoluminescence (PL) spectroscopy. In UV-Vis data, maximum values of 2H, Co, Cu, and Zn complexes were 708 nm and 677 nm, 686 nm, 684 nm, respectively.

Optical, morphological and structural characterization of Langmuir-Schaefer films of a functionalized copper phthalocyanine.

PubMed

Giancane, Gabriele; Filippo, Emanuela; Manno, Daniela; Serra, Antonio; Valli, Ludovico

2011-11-01

Langmuir-Schaefer (LS) films of copper(II) tetrakis-(isoprpoxy-carbonyl)-phthalocyanine (TiPCuPc) have been deposited onto various solid supports. Its floating film have been characterized at the air-water interface by means of Brewster Angle Microscopy and Langmuir curves. Vibrational modes of multilayer transferred LS film have been studied by Raman spectroscopy and the optical parameters (refractive index n and extinction coefficient k) have been determined in the visible range of the electromagnetic spectrum. Linearly polarized light absorbance measurements have been performed at room temperature in the 400-800 nm spectral range and the average orientation of the phthalocyanine rings have been estimated. Transmission electron microscopy has been also used to characterize the morphological properties of the LS film and a close packed arrangement of the deposited molecules has been observed. Copyright © 2011 Elsevier Inc. All rights reserved.

Crystal structures of bis-(phen-oxy)silicon phthalocyanines: increasing π-π inter-actions, solubility and disorder and no halogen bonding observed.

PubMed

Lessard, Benoît H; Lough, Alan J; Bender, Timothy P

2016-07-01

We report the syntheses and characterization of three solution-processable phen-oxy silicon phthalocyanines (SiPcs), namely bis-(3-methyl-phen-oxy)(phthalocyanine)silicon [(3MP)2-SiPc], C46H30N8O2Si, bis-(2-sec-butyl-phen-oxy)(phthalocyanine)silicon [(2secBP)2-SiPc], C44H24I2N8O2Si, and bis-(3-iodo-phen-oxy)(phthalocyanine)silicon [(3IP)2-SiPc], C52H42N8O2Si. Crystals grown of these compounds were characterized by single-crystal X-ray diffraction and the π-π inter-actions between the aromatic SiPc cores were studied. It was determined that (3MP)2-SiPc has similar inter-actions to previously reported bis-(3,4,5-tri-fluoro-phen-oxy)silicon phthalocyanines [(345 F)2-SiPc] with significant π-π inter-actions between the SiPc groups. (3IP)2-SiPc and (2secBP)2-SiPc both experienced a parallel stacking of two of the peripheral aromatic groups. In all three cases, the solubility of these mol-ecules was increased by the addition of phen-oxy groups while maintaining π-π inter-actions between the aromatic SiPc groups. The solubility of (2secBP)2-SiPc was significantly higher than other bis-phen-oxy-SiPcs and this was exemplified by the higher observed disorder within the crystal structure.

Cellular imaging using BODIPY-, pyrene- and phthalocyanine-based conjugates.

PubMed

Bizet, Faustine; Ipuy, Martin; Bernhard, Yann; Lioret, Vivian; Winckler, Pascale; Goze, Christine; Perrier-Cornet, Jean-Marie; Decréau, Richard A

2018-01-15

Fluorescent Probes aimed at absorbing in the blue/green region of the spectrum and emitting in the green/red have been synthesized (as the form of dyads-pentads), studied by spectrofluorimetry, and used for cellular imaging. The synthesis of phthalocyanine-pyrene 1 was achieved by cyclotetramerization of pyrenyldicyanobenzene, whereas phthalocyanine-BODIPY 2c was synthesized by Sonogashira coupling between tetraiodophthalocyanine and meso-alkynylBODIPY. The standard four-steps BODIPY synthesis was applied to the BODIPY-pyrene dyad 3 starting from pyrenecarbaldehyde and dimethylpyrrole. 1 H, 13 C, 19 F, 11 BNMR, ICP, MS, and UV/Vis spectroscopic analyses demonstrated that 2c is a mixture of BODIPY-Pc conjugates corresponding to an average ratio of 2.5 BODIPY per Pc unit, where its bis, tris, tetrakis components could not be separated. Fluorescence emission studies (μM concentration in THF) showed that the design of the probes allowed excitation of their antenna (pyrene, BODIPY) in the blue/green region of the spectrum, and subsequent transfer to the acceptor platform (BODIPY, phthalocyanine) followed by its emission in the green/red (with up to 140-350 nm overall Stokes shifts). The fluorescent probes were used for cellular imaging of B16F10 melanoma cells upon solubilization in 1% DMSO containing RPMI or upon encapsulation in liposomes (injection method). Probes were used at 1-10 μM concentrations, cells were fixed with methanol and imaged by biphoton and/or confocal microscopy, showing that probes could achieve the staining of cells membranes and not the nucleus. Copyright © 2017. Published by Elsevier Ltd.

Synthesis of phthalocyanine derivatives as materials for organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Collazo-Ramos, Aura

Organic photovoltaics (OPVs) are used to convert sunlight into electricity by using thin films of organic semiconductors. OPVs have the potential to produce low cost, lightweight, flexible devices with an eased manufacturing process. This technology contains the potential to increase the use of clean, sustainable solar energy, helping manage the global energy and environmental crisis that results majorly from the constant use of fossil fuels as an energy source. The ability to modulate the physical properties of organic molecules by tuning their chemical structure is an advantage for OPVs. Phthalocyanines (Pcs) are highly pi-conjugated synthetic porphyrin analogs that have been explored as active layer components in OPVs due to their high extinction coefficients and hole mobilities. The Pc structure can be modified by the introduction of metals in the core and the incorporation of substituents into the periphery. These modifications tend to tune the solubility, photophysical properties and condensed phase organization of Pcs. The research work in this dissertation describes improved methods towards substituted Pc derivatives addressing: (1) the use of mass spectrometry techniques for Pcs characterization, (2) efforts to achieve materials with near-infrared (NIR) absorption, and (3) the potential of Pc as electron-acceptor materials. Herein, the synthesis of a series of asymmetric and symmetric metallated Pcs has been established, which resulted in interesting chemical, photophysical and electrochemical properties. The materials investigated in this thesis increase the potential of Pcs as organic semiconductors for OPVs.

Ordering of Zn-centered porphyrin and phthalocyanine on TiO2(011): STM studies

PubMed Central

Godlewski, Szymon; Such, Bartosz; Pawlak, Rémy; Hinaut, Antoine; Jöhr, Res; Glatzel, Thilo; Meyer, Ernst; Szymonski, Marek

2017-01-01

Zn(II)phthalocyanine molecules (ZnPc) were thermally deposited on a rutile TiO2(011) surface and on Zn(II)meso-tetraphenylporphyrin (ZnTPP) wetting layers at room temperature and after elevated temperature thermal processing. The molecular homo- and heterostructures were characterized by high-resolution scanning tunneling microscopy (STM) at room temperature and their geometrical arrangement and degree of ordering are compared with the previously studied copper phthalocyanine (CuPc) and ZnTPP heterostructures. It was found that the central metal atom may play some role in ordering and growth of phthalocyanine/ZnTPP heterostructures, causing differences in stability of upright standing ZnPc versus CuPc molecular chains at given thermal annealing conditions. PMID:28144569

Fabrication and characterization of P3HT:PCBM-based thin film organic solar cells with zinc phthalocyanine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maruhashi, Haruto, E-mail: oku@mat.usp.ac.jp; Oku, Takeo, E-mail: oku@mat.usp.ac.jp; Suzuki, Atsushi, E-mail: oku@mat.usp.ac.jp

2015-02-27

[6,6]–phenyl C{sub 61}–butyric acid methyl ester and poly(3–hexylthiophene) bulk heterojunction solar cells added with zinc–tetra–tertiary–butyl–phthalocyanine (ZnPc) were fabricated and characterized. The photovoltaic properties of the solar cells with an inverted structure were improved by the ZnPc addition, which were investigated on the bases of current density–voltage characteristics, incident photon to current conversion efficiency.

Preparation and Characterization of Cu and Ni on Alumina Supports and Their Use in the Synthesis of Low-Temperature Metal-Phthalocyanine Using a Parallel-Plate Reactor

PubMed Central

Sánchez-De la Torre, Fernando; De la Rosa, Javier Rivera; Kharisov, Boris I.; Lucio-Ortiz, Carlos J.

2013-01-01

Ni- and Cu/alumina powders were prepared and characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), and N2 physisorption isotherms were also determined. The Ni/Al2O3 sample reveled agglomerated (1 μm) of nanoparticles of Ni (30–80 nm) however, NiO particles were also identified, probably for the low temperature during the H2 reduction treatment (350 °C), the Cu/Al2O3 sample presented agglomerates (1–1.5 μm) of nanoparticles (70–150 nm), but only of pure copper. Both surface morphologies were different, but resulted in mesoporous material, with a higher specificity for the Ni sample. The surfaces were used in a new proposal for producing copper and nickel phthalocyanines using a parallel-plate reactor. Phthalonitrile was used and metallic particles were deposited on alumina in ethanol solution with CH3ONa at low temperatures; ≤60 °C. The mass-transfer was evaluated in reaction testing with a recent three-resistance model. The kinetics were studied with a Langmuir-Hinshelwood model. The activation energy and Thiele modulus revealed a slow surface reaction. The nickel sample was the most active, influenced by the NiO morphology and phthalonitrile adsorption. PMID:28788334

Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

NASA Astrophysics Data System (ADS)

Zhao, Na; Li, Siwen; Wang, Jinyi; Zhang, Ronglan; Gao, Ruimin; Zhao, Jianshe; Wang, Junlong

2015-05-01

M2(PcAN)2 (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M2(PcAN)2-W-HZSM-5) or the M2(PcTN)2 doping W-HZSM-5 (M2(PcTN)2/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu2(PcAN)2-W-HZSM-5 and Cu2(PcTN)2/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV-Vis and calcination temperature was obtained by TG-DSC for Cu2(PcTN)2/W-HZSM-5. Catalysts were characterized by EA, IR, XRD, SEM, TEM, ICP, and N2 adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. The reaction process of ultra-deep desulfurization.

Synthesis of axially disubstituted silicon phthalocyanines and investigation of photodynamic effects on HCT-116 colorectal cancer cell line.

PubMed

Sarı, Ceren; Eyüpoğlu, Figen Celep; Değirmencioğlu, İsmail; Bayrak, Rıza

2018-05-15

Photodynamic therapy is one of the hot topics in cancer studies recently. Basically, photosensitizing chemical substrates which are stimulated by light having a specific wavelength cause fatal effect on different kind of cells in photodynamic therapy. In this study, axially 4-{[(1E)-2-furylmethylene]amino}phenol, 4-{[(1E)-2-thienylmethylene]amino}phenol and 4-{[(1E)-(4-nitro-2-thienyl)methylene]amino}phenol disubstituted silicon phthalocyanines were synthesized as Photosensitizers for photodynamic therapy in cancer treatment for the first time. The structural characterizations of these novel compounds were performed by a combination of FT-IR, 1 H-NMR, UV-vis and mass. All these newly prepared compounds did not show aggregation at the concentration range of 2 × 10 -6 -12 × 10 -6 M in tetrahydrofurane and also did not show aggregation in different organic solvents at 2 × 10 -6 M concentration. Phthalocyanines which are synthesized in this study are tested on HCT-116 colorectal cancer cells and stimulated by light has wavelength of 680 nm. The toxic effects on cancer cells which are caused by different concentrations of photosensitizing molecules have been examined and compared with the toxic effects on cancer cells that were kept in the dark. It is confirmed that these molecules caused toxic effects on colorectal cancer cells when they were stimulated by light but there was no toxic effect in the dark. Copyright © 2018. Published by Elsevier B.V.

Spectroscopic characterization of zirconium(IV) and hafniumf(IV) gallate phthalocyanines in monolithic silica gels obtained by sol gel method

NASA Astrophysics Data System (ADS)

Gerasymchuk, Y. S.; Chernii, V. Ya.; Tomachynski, L. A.; Legendziewicz, J.; Radzki, St.

2005-07-01

The Zr(IV) and Hf(IV) phthalocyanines, with gallate as axial ligand coordinated to the central metal atom of phthalocyanine, were incorporated in silica gels during sol-gel process with using tetraethyl orthosilicate (TEOS) as precursor. The obtained mixed inorganic-organic composites were transparent and homogeneous. The absorption and emission properties of these materials in comparison with the spectra of the Zr(IV) and Hf(IV) phthalocyanines in various solvents were investigated. The spectra were correlated with various stage of the sol-gel process. It was established that in the gels concurrence of the monomer and dimer form is different in sol, alco-, hydro- and xerogels. The intensive 700-725 nm fluorescence emission upon relatively long-wavelength excitation and unusually large (about 45 nm) Stokes shift in the Q region, suggest that Zr(IV) and Hf(IV) phthalocyanines could be considered as photosensitizers in the PDT method (photodynamic therapy).

Functionalized copper(II)-phthalocyanine in solution and as thin film: photochemical and morphological characterization toward applications.

PubMed

Ingrosso, Chiara; Curri, M Lucia; Fini, Paola; Giancane, Gabriele; Agostiano, Angela; Valli, Ludovico

2009-09-01

This article reports on an extensive investigation on a functionalized phthalocyanine, namely, copper(II) tetrakis-(isopropoxy-carbonyl)-phthalocyanine (TIPCuPc). The self-association of the molecules is extensively described in solution in different solvents (DMSO, DMF, CHCl(3), pyridine) by means of UV-vis steady state spectroscopy at the air/water interface by Brewster angle microscopy (BAM) and in thin films by using atomic force microscopy (AFM). We investigated the morphology of TIPCuPc as thin film by evaluating different factors: temperature, solvent, concentration, transferring procedure (spin-coating and Langmuir-Schafer technique), and nature of the substrate (mica and quartz). The behavior of the molecules under UV light irradiation and their thermal stability were studied as well. Such a detailed study can allow a suitable processing of this phthalocyanine derivative for future applications. Here the photoelectrochemical activity of the phthalocyanine was investigated when suitably combined as sensitizer with rodlike TiO(2) nanocrystals (NCs) in hybrid junctions integrated in a photoelectrochemical cell.

Natural gum-assisted phthalocyanine immobilization in electroactive nanocomposites: physicochemical characterization and sensing applications.

PubMed

Zampa, Maysa F; de Brito, Ana Cristina F; Kitagawa, Igor L; Constantino, Carlos J L; Oliveira, Osvaldo N; da Cunha, Helder N; Zucolotto, Valtencir; dos Santos, José Ribeiro; Eiras, Carla

2007-11-01

Natural gums have been traditionally applied in cosmetics and the food industry, mainly as emulsification agents. Due to their biodegradability and excellent mechanical properties, new technological applications have been proposed involving their use with conventional polymers forming blends and composites. In this study, we take advantage of the polyelectrolyte character exhibited by the natural gum ChichA (Sterculia striata), extracted in the Northeastern region of Brazil, to produce electroactive nanocomposites. The nanocomposites were fabricated in the form of ultrathin films by combining a metallic phthalocyanine (nickel tetrasulfonated phthalocyanine, NiTsPc) and the ChichA gum in a tetralayer architecture, in conjunction with conventional polyelectrolytes. The presence of the gum led to an efficient adsorption of the phthalocyanine and enhanced the electrochemical response of the films. Upon combining the electrochemical and UV-vis absorption data, energy diagrams of the ChichA/NiTsPc-based system were obtained. Furthermore, modified electrodes based on gum/phthalocyanine films were able to detect dopamine at concentrations as low as 10-5 M.

In vitro photodynamic activity of lipid vesicles with zinc phthalocyanine derivative against Enterococcus faecalis.

PubMed

Sobotta, Lukasz; Dlugaszewska, Jolanta; Kasprzycki, Piotr; Lijewski, Sebastian; Teubert, Anna; Mielcarek, Jadwiga; Gdaniec, Maria; Goslinski, Tomasz; Fita, Piotr; Tykarska, Ewa

2018-06-01

Zinc(II) phthalocyanine bearing eight non-peripheral 2-propoxy substituents was subjected to physicochemical study and, after incorporation in lipid vesicles, assessed as a potential photosensitizer for antibacterial photodynamic therapy. The phthalocyanine derivative obtained in the macrocyclization reaction was characterized by MS and NMR techniques. Moreover, its chemical purity was confirmed by HPLC analysis. X-ray structural analysis revealed that overcrowding of the phthalocyanine derivative leads to a strong out-of-plane distortion of the π-system of the macrocycle core. In the UV-Vis absorption spectra of zinc(II) phthalocyanine two characteristic bands were found: the Soret (300-450 nm) and the Q band (600-800 nm). Photophysical properties of mono- and diprotonated forms of phthalocyanine derivative were studied with time-resolved fluorescence spectroscopy. Its tri- and tetraprotonated forms could not be obtained, because compound decomposes in higher acid concentrations. The presented zinc(II) phthalocyanine showed values of singlet oxygen generation Φ Δ  = 0.18 and 0.16, the quantum yield of the photodecomposition Φ P  = 3.06∙10 -4 and 1.23∙10 -5 and the quantum yield of fluorescence Φ FL  = 0.005 and 0.004, designated in DMF and DMSO, respectively. For biological studies, phthalocyanine has been incorporated into modified liposome vesicles containing ethanol. In vitro bacteria photoinactivation study revealed no activity against Escherichia coli and 5.7 log reduction of the Enterococcus faecalis growth. Copyright © 2018 Elsevier B.V. All rights reserved.

Preparation and In Vitro Photodynamic Activity of Glucosylated Zinc(II) Phthalocyanines as Underlying Targeting Photosensitizers.

PubMed

Liu, Jian-Yong; Wang, Chen; Zhu, Chun-Hui; Zhang, Zhi-Hong; Xue, Jin-Ping

2017-05-19

Two novel glucosylated zinc(ІІ) phthalocyanines 7a-7b, as well as the acetyl-protected counterparts 6a-6b, have been synthesized by the Cu(I)-catalyzed 1,3-dipolar cycloaddition between the propargylated phthalocyanine and azide-substituted glucoses. All of these phthalocyanines were characterized with various spectroscopic methods and studied for their photo-physical, photo-chemical, and photo-biological properties. With glucose as the targeting unit, phthalocyanines 7a-7b exhibit a specific affinity to MCF-7 breast cancer cells over human embryonic lung fibroblast (HELF) cells, showing higher cellular uptake. Upon illumination, both photosensitizers show high cytotoxicity with IC 50 as low as 0.032 µM toward MCF-7 cells, which are attributed to their high cellular uptake and low aggregation tendency in the biological media, promoting the generation of intracellular reactive oxygen species (ROS). Confocal laser fluorescence microscopic studies have also revealed that they have high and selective affinities to the lysosomes, but not the mitochondria, of MCF-7 cells. The results show that these two glucosylated zinc(II) phthalocyanines are potential anticancer agents for targeting photodynamic therapy.

Phthalocyanines functionalized with 2-methyl-5-nitro-1H-imidazolylethoxy and 1,4,7-trioxanonyl moieties and the effect of metronidazole substitution on photocytotoxicity.

PubMed

Wierzchowski, Marcin; Sobotta, Lukasz; Skupin-Mrugalska, Paulina; Kruk, Justyna; Jusiak, Weronika; Yee, Michael; Konopka, Krystyna; Düzgüneş, Nejat; Tykarska, Ewa; Gdaniec, Maria; Mielcarek, Jadwiga; Goslinski, Tomasz

2013-10-01

Four novel magnesium(II) and zinc(II) phthalocyanines bearing 1,4,7-trioxanonyl, polyether and/or (2-methyl-5-nitro-1H-imidazol-1-yl)ethoxy, heterocyclic substituents at their non-peripheral positions were synthesized and assessed in terms of physicochemical and biological properties. Magnesium phthalocyanine derivatives bearing polyether substituents (Pc-1), a mixed system of polyether and heterocyclic substituents (Pc-3), and four heterocyclic substituents (Pc-4), respectively, were synthesized following the Linstead macrocyclization reaction procedure. Zinc phthalocyanine (Pc-2) bearing polyether substituents at non-peripheral positions was synthesized following the procedure in n-pentanol with the zinc acetate, and DBU. Novel phthalocyanines were purified by flash column chromatography and characterized using NMR, MS, UV-Vis and HPLC. Moreover, two precursors in macrocyclization reaction phthalonitriles were characterized using X-ray. Photophysical properties of the novel macrocycles were evaluated, including UV-Vis spectra analysis and aggregation study. All macrocycles subjected to singlet oxygen generation and the oxidation rate constant measurements exhibited lower quantum yields of singlet oxygen generation in DMSO than in DMF. In addition, the Pc-2 molecule was found to be the most efficient singlet oxygen generator from the group of macrocycles studied. The photocytotoxicity evaluated on the human oral squamous cell carcinoma cell line, HSC-3, for Pc-3 was significantly higher than that for Pc-1, Pc-2, and Pc-4. Interestingly, Pc-3 was found to be the most active macrocycle in vitro although its ability to generate singlet oxygen was significantly lower than those of Pc-1 and Pc-2. However, attempts to encapsulate phthalocyanines Pc-1-Pc-3 in liposomal membranes were unsuccessful. The phthalocyanine-nitroimidazole conjugate, Pc-4 was encapsulated in phosphatidylglycerol:phosphatidylcholine unilamellar liposomes and subjected to photocytotoxicity study. © 2013.

Photophysicochemical behaviour and antimicrobial properties of monocarboxy Mg (II) and Al (III) phthalocyanine-magnetite conjugates

NASA Astrophysics Data System (ADS)

Idowu, Mopelola Abidemi; Xego, Solami; Arslanoglu, Yasin; Mark, John; Antunes, Edith; Nyokong, Tebello

2018-03-01

Asymmetric Mg (II) or Al (III) phthalocyanine (containing a COOH group and 3-pyridylsulfanyl units) was conjugated via an amide bond to amino functionalized magnetic nanoparticle (AIMN) to form MgPc-AIMN or AlPc-AIMN conjugate, and characterized. The photophysicochemical behaviour of the phthalocyanine-AIMN conjugates was investigated and compared to the asymmetric Pcs and to the simple mixture of Pc with AIMNs without a chemical bond, (MPc-AIMN (mixed)). The directed covalent linkage of AIMNs to the asymmetrical metallopthalocyanines afforded improvements in the singlet oxygen (VΔ) and triplet state quantum yield (VT) as well as singlet oxygen lifetimes for the MPcs-AIMN-linked conjugates compared to MPc-AIMN (mixed) and MPcs alone. The asymmetric phthalocyanines and their conjugates showed effective antimicrobial activity against Escherichia coli bacteria under illumination.

Near Infrared Phosphorescent, Non-oxidizable Palladium and Platinum Perfluoro-phthalocyanines.

PubMed

Łapok, Łukasz; Obłoza, Magdalena; Gorski, Alexandr; Knyukshto, Valeri; Raichyonok, Tamara; Waluk, Jacek; Nowakowska, Maria

2016-04-18

New Pd(II) and Pt(II) complexes with a highly electron-deficient ligand (H2 PcF64 ) were conveniently prepared in a three-step synthesis. This is the first time that the phosphorescence of phthalocyanines with a H2 PcF64 framework has been measured. Based on these measurements, the triplet-state energies (ET ) were directly determined. Transient absorption experiments revealed broad T1 →Tn absorption spanning from ca. 350 to ca. 1000 nm and allowed determination of the triplet-state lifetimes. Removal of the Pd or Pt from the perfluoro-phthalocyanine resulted in a significant increase of the triplet lifetime for H2 PcF64 . The very efficient intersystem crossing observed for both PdPcF64 and PtPcF64 leads to residual fluorescence and suppresses the fluorescence lifetimes to less than 50 ps. The absence of Pd and Pt in the perfluoro-phthalocyanine ligand, viz. H2 PcF64 , led to a recovery of fluorescence. Cyclic voltamperometry studies pointed to complete resistance of PdPcF64 and PtPcF64 to oxidation and very strong electron affinity, which rendered these materials very good electron acceptors (n-type materials). The presence of d-orbital metals such as Pd(II) and Pt(II) in the phthalocyanine ring stabilizes their reduced forms, as indicated by the spectroelectrochemical experiments. PdPcF64 and PtPcF64 easily sensitize singlet oxygen production with very high quantum yields. Both phthalocyanines presented resistance to photodegradation in the solid state under aerobic conditions and under intense irradiation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal selectivity of intermolecular versus intramolecular reactions on surfaces

PubMed Central

Cirera, Borja; Giménez-Agulló, Nelson; Björk, Jonas; Martínez-Peña, Francisco; Martin-Jimenez, Alberto; Rodriguez-Fernandez, Jonathan; Pizarro, Ana M.; Otero, Roberto; Gallego, José M.; Ballester, Pablo; Galan-Mascaros, José R.; Ecija, David

2016-01-01

On-surface synthesis is a promising strategy for engineering heteroatomic covalent nanoarchitectures with prospects in electronics, optoelectronics and photovoltaics. Here we report the thermal tunability of reaction pathways of a molecular precursor in order to select intramolecular versus intermolecular reactions, yielding monomeric or polymeric phthalocyanine derivatives, respectively. Deposition of tetra-aza-porphyrin species bearing ethyl termini on Au(111) held at room temperature results in a close-packed assembly. Upon annealing from room temperature to 275 °C, the molecular precursors undergo a series of covalent reactions via their ethyl termini, giving rise to phthalocyanine tapes. However, deposition of the tetra-aza-porphyrin derivatives on Au(111) held at 300 °C results in the formation and self-assembly of monomeric phthalocyanines. A systematic scanning tunnelling microscopy study of reaction intermediates, combined with density functional calculations, suggests a [2+2] cycloaddition as responsible for the initial linkage between molecular precursors, whereas the monomeric reaction is rationalized as an electrocyclic ring closure. PMID:26964764

Photophysical, photochemical and BSA binding/BQ quenching properties of quaternizable coumarin containing water soluble zinc phthalocyanine complexes

NASA Astrophysics Data System (ADS)

Esenpınar, Aliye Aslı; Durmuş, Mahmut; Bulut, Mustafa

2011-08-01

The non-peripherally ( np-QZnPc) and peripherally ( p-QZnPc) tetrakis-[7-oxo-(3-[(2-diethylaminomethyliodide)ethyl)]-4-methylcoumarin]-phthalocyaninatozinc complexes have been prepared by quaternization of non-peripherally and peripherally tetrakis[7-oxo-(3-[(2-diethylamino)ethyl)]-methylcoumarin] phthalocyaninato zinc complexes with methyliodide in dimethylsulfoxide (DMSO). The new quaternized zinc phthalocyanine complex ( np-QZnPc) has been characterized by elementel analysis, MALDI-TOF, IR and UV-vis spectral data. The photophysical and photochemical properties of the peripherally and non-peripherally quaternized tetrakis-3-[(2-diethylamino)ethyl]-7-oxo-4-methylcoumarin substituted zinc phthalocyanines are reported. The effects of the position of the substituents and the aggregation of the phthalocyanine molecules on the photophysical and photochemical properties are also investigated. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes for complexes np-ZnPc/ p-ZnPc in DMSO and for complexes np-QZnPc/p-QZnPc in DMSO, phosphate buffered solution (PBS) and PBS+Triton-X 100 solutions. The fluorescence of the tetra-substituted quaternized zinc phthalocyanine complexes ( np-QZnPc/ p-QZnPc) are effectively quenched addition of 1,4-benzoquinone (BQ) and this study also presented the ionic zinc phthalocyanine complexes strongly bind to bovine serum albumin (BSA).

Antimicrobial and anticancer photodynamic activity of a phthalocyanine photosensitizer with N-methyl morpholiniumethoxy substituents in non-peripheral positions.

PubMed

Dlugaszewska, Jolanta; Szczolko, Wojciech; Koczorowski, Tomasz; Skupin-Mrugalska, Paulina; Teubert, Anna; Konopka, Krystyna; Kucinska, Malgorzata; Murias, Marek; Düzgüneş, Nejat; Mielcarek, Jadwiga; Goslinski, Tomasz

2017-07-01

Photodynamic therapy involves the use of a photosensitizer that is irradiated with visible light in the presence of oxygen, resulting in the formation of reactive oxygen species. A novel phthalocyanine derivative, the quaternary iodide salt of magnesium(II) phthalocyanine with N-methyl morpholiniumethoxy substituents, was synthesized, and characterized. The techniques used included mass spectrometry (MALDI TOF), UV-vis, NMR spectroscopy, and photocytotoxicity against bacteria, fungi and cancer cells. The phthalocyanine derivative possessed typical characteristics of compounds of the phthalocyanine family but the effect of quaternization was observed on the optical properties, especially in terms of absorption efficiency. The results of the photodynamic antimicrobial effect study demonstrated that cationic phthalocyanine possesses excellent photodynamic activity against planktonic cells of both Gram-positive and Gram-negative bacteria. The bactericidal effect was dose-dependent and all bacterial strains tested were killed to a significant degree by irradiated phthalocyanine at a concentration of 1×10 -4 M. There were no significant differences in the susceptibility of Gram-positive and Gram-negative bacteria to the applied photosensitizer. The photosensitivity of bacteria in the biofilm was lower than that in planktonic form. No correlation was found between the degree of biofilm formation and susceptibility to antimicrobial photodynamic inactivation. The anticancer activity of the novel phthalocyanine derivative was tested using A549 adenocarcinomic alveolar basal epithelial cells and the human oral squamous cell carcinoma cells derived from tongue (HSC3) or buccal mucosa (H413). No significant decrease in cell viability was observed under different conditions or with different formulations of the compound. Copyright © 2017 Elsevier Inc. All rights reserved.

Development of a matrix-assisted laser desorption ionization mass spectrometric method for rapid process-monitoring of phthalocyanine compounds.

PubMed

Chen, Yi-Ting; Wang, Fu-Shing; Li, Zhendong; Li, Liang; Ling, Yong-Chien

2012-07-29

Phthalocyanines (PCs), an important class of chemicals widely used in many industrial sectors, are macrocyclic compounds possessing a heteroaromatic π-electron system with optical properties influenced by chemical structures and impurities or by-products introduced during the synthesis process. Analytical tools allowing for rapid monitoring of the synthesis processes are of significance for the development of new PCs with improved performance in many application areas. In this work, we report a matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry (TOFMS) method for rapid and convenient monitoring of PC synthesis reactions. For this class of compounds, intact molecular ions could be detected by MALDI using retinoic acid as matrix. It was shown that relative quantification results of two PC compounds could be generated by MALDI MS. This method was applied to monitor the bromination reactions of nickel- and copper-containing PCs. It was demonstrated that, compared to the traditional UV-visible method, the MALDI MS method offers the advantage of higher sensitivity while providing chemical species and relative quantification information on the reactants and products, which are crucial to process monitoring. Copyright © 2012 Elsevier B.V. All rights reserved.

Improved selectivity towards NO₂ of phthalocyanine-based chemosensors by means of original indigo/nanocarbons hybrid material.

PubMed

Brunet, J; Pauly, A; Dubois, M; Rodriguez-Mendez, M L; Ndiaye, A L; Varenne, C; Guérin, K

2014-09-01

A new and original gas sensor-system dedicated to the selective monitoring of nitrogen dioxide in air and in the presence of ozone, has been successfully achieved. Because of its high sensitivity and its partial selectivity towards oxidizing pollutants (nitrogen dioxide and ozone), copper phthalocyanine-based chemoresistors are relevant. The selectivity towards nitrogen dioxide results from the implementation of a high efficient and selective ozone filter upstream the sensing device. Thus, a powdered indigo/nanocarbons hybrid material has been developed and investigated for such an application. If nanocarbonaceous material acts as a highly permeable matrix with a high specific surface area, immobilized indigo nanoparticles are involved into an ozonolysis reaction with ozone leading to the selective removal of this analytes from air sample. The filtering yields towards each gas have been experimentally quantified and establish the complete removal of ozone while having the concentration of nitrogen dioxide unchanged. Long-term gas exposures reveal the higher durability of hybrid material as compared to nanocarbons and indigo separately. Synthesis, characterizations by many complementary techniques and tests of hybrid filters are detailed. Results on sensor-system including CuPc-based chemoresistors and indigo/carbon nanotubes hybrid material as in-line filter are illustrated. Sensing performances will be especially discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, supramolecular behavior, and in vitro photodynamic activities of novel zinc(II) phthalocyanines "side-strapped" with crown ether bridges.

PubMed

Chen, Xing-Wei; Ke, Mei-Rong; Li, Xing-Shu; Lan, Wen-Liang; Zhang, Miao-Fen; Huang, Jian-Dong

2013-12-01

Two new tetra- or di-α-substituted zinc(II) phthalocyanines 5 and 6 have been prepared through a "side-strapped" method. In the molecules, the adjacent benzene rings of the phthalocyanine core are linked at α-position through a triethylene glycol bridge to form a hybrid aza-/oxa-crown ether. The tetra-α-substituted phthalocyanine 5 shows an eclipsed self-assembly property in CH2Cl2 and the effect on the di-α-substituted analogue 6 is significantly weakened. Furthermore, the crown ethers of these compounds can selectively complex with Fe(3+) or Cu(2+) ion in DMF, leading to formation of J-aggregated nano-assemblies, which can be disaggregated in the presence of some organic or inorganic ligands, such as triethylamine, tetramethylethylenediamine, CH3COO(-), or OH(-). In addition, both compounds are efficient singlet oxygen generators with the singlet oxygen quantum yields (Φ(Δ)) of 0.54-0.74 in DMF relative to unsubstituted zinc(II) phthalocyanine (Φ(Δ)=0.56). They exhibit photodynamic activities toward HepG2 human hepatocarcinoma cells, but the compound 6, which has more than 40-fold lower IC50 value (0.08 μM) compared to the analogue 5 (IC50=3.31 μM), shows remarkablely higher in vitro photocytotoxicity due to its significantly higher cellular uptake and singlet oxygen generation efficiency. The results suggest that these compounds can serve as promising multifunctional materials both in (opto)electronic field and photodynamic therapy. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design, synthesis, characterization, and OFET properties of amphiphilic heteroleptic tris(phthalocyaninato) europium(III) complexes. The effect of crown ether hydrophilic substituents.

PubMed

Gao, Yingning; Ma, Pan; Chen, Yanli; Zhang, Ying; Bian, Yongzhong; Li, Xiyou; Jiang, Jianzhuang; Ma, Changqin

2009-01-05

Two amphiphilic heteroleptic tris(phthalocyaninato) europium complexes with hydrophilic crown ether heads and hydrophobic octyloxy tails [Pc(mCn)(4)]Eu[Pc(mCn)(4)]Eu[Pc(OC(8)H(17))(8)] [m = 12, n = 4, H(2)Pc(12C4)(4) = 2,3,9,10,16,17,23,24-tetrakis(12-crown-4)phthalocyanine; m = 18, n = 6, H(2)Pc(18C6)(4) = 2,3,9,10,16,17,23,24-tetrakis(18-crown-6)phthalocyanine; H(2)Pc(OC(8)H(17))(8) = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] (1, 2) were designed and prepared from the reaction between homoleptic bis(phthalocyaninato) europium compound [Pc(mCn)(4)]Eu[Pc(mCn)(4)] (m = 12, n = 4; m = 18, n = 6) and metal-free H(2)Pc(OC(8)H(17))(8) in the presence of Eu(acac)(3).H(2)O (Hacac = acetylacetone) in boiling 1,2,4-trichlorobenzene. These novel sandwich triple-decker complexes were characterized by a wide range of spectroscopic methods and electrochemically studied. With the help of the Langmuir-Blodgett technique, these typical amphiphilic triple-decker complexes were fabricated into organic field effect transistors (OFET) with top contact configuration on bare SiO(2)/Si substrate, hexamethyldisilazane-treated SiO(2)/Si substrate, and octadecyltrichlorosilane (OTS)-treated SiO(2)/Si substrate, respectively. The device performance is revealed to be dependent on the species of crown ether substituents and substrate surface treatment. OFETs fabricated from the triple decker with 12-crown-4 hydrophilic substituents, 1, allow the hole transfer in the direction parallel to the aromatic phthalocyanine rings. In contrast, the devices of a triple-decker compound containing 18-crown-6 as hydrophilic heads, 2, transfer holes in a direction along the long axis of the assembly composed of face-to-face aggregated triple-decker molecules, revealing the effect of molecular structure, specifically the crown ether substituents on the film structure and OFET functional properties. The carrier mobility for hole as high as 0.33 cm(2) V(-1) s(-1) and current modulation of 7.91 x 10(5) were reached for the devices of triple-decker compound 1 deposited on the OTS-treated SiO(2)/Si substrates, indicating the effect of substrate surface treatment on the OFET performance due to the improvement on the film quality as demonstrated by the atomic force microscope investigation results.

Indium-chlorine and gallium-chlorine tetrasubstituted phthalocyanines in a bulk system, Langmuir monolayers and Langmuir-Blodgett nanolayers--spectroscopic investigations.

PubMed

Bursa, B; Wróbel, D; Biadasz, A; Kędzierski, K; Lewandowska, K; Graja, A; Szybowicz, M; Durmuş, M

2014-07-15

The paper deals with spectroscopic characterization of metallic phthalocyanines (Pc's) (indium and gallium) complexed with chlorine and substituted with four benzyloxyphenoxy peripheral groups in bulk systems, 2D Langmuir monolayers and Langmuir-Blodgett nanolayers. An influence of the molecular structure of dyes (the presence of metal and of substitutes attached to the phthalocyanine macroring) on the in situ measurements of light absorption is reported. Molecular arrangement of the phthalocyanine molecular skeleton in the Langmuir monolayers on water substrate and in the Langmuir-Blodgett nanolayers is evaluated. A comparison of the light absorption spectra of the phthalocyanine monolayers with the spectra of the dyes in solution supports the existence of dye aggregates in the monolayer. It was shown that the type of dye aggregates (oblique and H types) depends markedly on the dye molecular structures. The NIR-IR, IR reflection-absorption and Raman spectra are also monitored for Langmuir-Blodgett nanolayers in non-polarized and polarized light. It was shown that the dye molecules in the Langmuir-Blodgett layers are oriented nearly vertically with respect to a gold substrate. Copyright © 2014 Elsevier B.V. All rights reserved.

Silicon Phthalocyanines Axially Disubstituted with Erlotinib toward Small-Molecular-Target-Based Photodynamic Therapy.

PubMed

Chen, Juan-Juan; Huang, Yi-Zhen; Song, Mei-Ru; Zhang, Zhi-Hong; Xue, Jin-Ping

2017-09-21

Small-molecular-target-based photodynamic therapy-a promising targeted anticancer strategy-was developed by conjugating zinc(II) phthalocyanine with a small-molecular-target-based anticancer drug. To prevent self-aggregation and avoid problems of phthalocyanine isomerization, two silicon phthalocyanines di-substituted axially with erlotinib have been synthesized and fully characterized. These conjugates are present in monomeric form in various solvents as well as culture media. Cell-based experiments showed that these conjugates localize in lysosomes and mitochondria, while maintaining high photodynamic activities (IC 50 values as low as 8 nm under a light dose of 1.5 J cm -2 ). With erlotinib as the targeting moiety, two conjugates were found to exhibit high specificity for EGFR-overexpressing cancer cells. Various poly(ethylene glycol) (PEG) linker lengths were shown to have an effect on the photophysical/photochemical properties and on in vitro phototoxicity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnO and cobalt phthalocyanine hybridized graphene: efficient photocatalysts for degradation of rhodamine B

PubMed Central

Neelgund, Gururaj M.; Oki, Aderemi; Luo, Zhiping

2014-01-01

A novel method has been developed to synthesize graphene-ZnO composite as a highly efficient catalyst by reduction of graphite oxide and in-situ deposition of ZnO nanoparticles by chemical reduction reaction. The graphene-ZnO catalyst is capable of complete degradation of rhodamine B under exposure to natural sunlight. Further, the catalytic efficiency of graphene-ZnO catalyst was enhanced by sensitizing with cobalt phthalocyanine. The formation of graphene-ZnO pcatalyst and its further sensitization with cobalt phthalocyanine was characterized using UV-vis, ATR-IR and Raman spectroscopy, powder XRD and thermogravimetric analysis. The morphology of both graphene-ZnO and graphene-ZnO-CoPC catalysts was analyzed using scanning and transmission electron microscopes. PMID:24972296

Photophysicochemical, calf thymus DNA binding and in vitro photocytotoxicity properties of tetra-morpholinoethoxy-substituted phthalocyanines and their water-soluble quaternized derivatives.

PubMed

Koçan, Halit; Kaya, Kerem; Özçeşmeci, İbrahim; Sesalan, B Şebnem; Göksel, Meltem; Durmuş, Mahmut; Burat, Ayfer Kalkan

2017-12-01

In this study, morpholinoethoxy-substituted metal-free (3), zinc(II) (4) and indium(III) (5) phthalocyanines were synthesized. These phthalocyanines were converted to their water-soluble quaternized derivatives (3Q-5Q) using excess methyl iodide as a quaternization agent. All these phthalocyanines (Pcs) were characterized by elemental analysis and different spectroscopic methods such as FT-IR, 1 H NMR, UV-Vis and mass spectrometry. The photophysical and photochemical properties such as fluorescence and generation of singlet oxygen were investigated for determination of these phthalocyanines as photosensitizers in photodynamic therapy (PDT) applications. The binding properties of quaternized phthalocyanines (3Q-5Q) to calf thymus DNA (CT-DNA) were investigated by UV-Vis and fluorescence spectrophotometric methods. The quenching effect of all quaternized phthalocyanines on the fluorescence intensity of SYBR Green-DNA complex was determined. The mixtures of 3Q, 4Q or 5Q and DNA solutions were used to determine the change in T m of double helix DNA with thermal denaturation profile. In addition, thermodynamic parameters considering their aggregation in buffer solution, which shows the spontaneity of the reactions between DNA and quaternized Pcs were investigated. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method. Peripherally tetra-substituted neutral and quaternized metal-free and metallophthalocyanines (MPcs) (Zn, In) bearing morpholinoethoxy groups were prepared. The binding of quaternized compounds (3Q-5Q) to CT-DNA were examined using UV-Vis, fluorescence spectra, thermal denaturation profiles and K SV values. Besides, thermodynamic studies indicated that binding of 3Q-5Q to DNA was spontaneous. On the other hand, in vitro phototoxicity and cytotoxicity behavior of the quaternized water-soluble phthalocyanine photosensitizers (3Q-5Q) were tested against the cervical cancer cell line named HeLa for evaluation of their suitability for treatment of cancer by PDT method.

Characterization of the interface interaction of cobalt on top of copper- and iron-phthalocyanine.

PubMed

Schmitt, Felix; Sauther, Jens; Lach, Stefan; Ziegler, Christiane

2011-05-01

The electronic structure of the interface between ferromagnetic cobalt and the organic semiconductors copper- (CuPc) and iron-phthalocyanine (FePc) was investigated by means of photoemission spectroscopy (UPS, IPES, and XPS). These metal-phthalocyanine (MePc) molecules have an open shell structure and are known to show promising properties for their use in organic spintronics. In spintronic devices, the interface between ferromagnetic electrode and the organic layer determines the spin injection properties and is hence important for the quality of, e.g., a possible spin-valve device. For this purpose, cobalt was deposited onto the MePcs, such as in devices with ferromagnetic top contacts. The reported investigations reveal a diffusion of cobalt into the organic layers and chemical reactions at the interface.

NIR photocleavage of the Si-C bond in axial Si-phthalocyanines.

PubMed

Doane, Tennyson; Cheng, Yu; Sodhi, Nipun; Burda, Clemens

2014-11-13

The use of light-triggered photolysis provides a powerful tool for unique syntheses and for applications that require remote operation such as drug delivery or molecular switches. Here, we describe the photochemistry of a recently developed alkylsilicon phthalocyanine Pc 227, which undergoes an exchange of the alkyl ligand for a ligand derived from the solvent when the axial Si-C bond is photolyzed in a solvent with low-energy visible light. In this work with methanol as the solvent, we investigate the formation of the methoxy analogue of the therapeutic drug Pc 4, (termed Pc 233) upon irradiation. Using steady-state spectroscopy and characterization of the photoproducts, the competing pathways between direct ligand exchange on the central silicon atom and delocalization of the radical produced by homolysis on the phthalocyanine ring is observed. The delocalized radical intermediate is quite long-lived. At long times this intermediate decomposes without significant formation of Pc 233. The results of this investigation provide insights into recent work utilizing Pc 227 for drug delivery applications and for future work on the use of phthalocyanines as long-wavelength phototriggers.

Synthesis of phthalocyanine doped sol-gel materials

NASA Technical Reports Server (NTRS)

Dunn, Bruce

1993-01-01

The synthesis of sol-gel silica materials doped with three different types of metallophthalocyanines has been studied. Homogeneous materials of good optical quality were prepared and the first optical limiting measurements of dyes in sol-gel hosts were carried out. The properties of these solid state limiters are similar to limiters based on phthalocyanine (Pc) in solution. Sol-gel silica materials containing copper, tin and germanium phthalocyanines were investigated. The initial step in all cases was to prepare silica sols by the sonogel method using tetramethoxy silane (TMOS), HCl and distilled water. Thereafter, the synthesis depended upon the specific Pc and its solubility characteristics. Copper phthalocyanine tetrasulfonic acid tetra sodium salt (CuPc4S) is soluble in water and various doping levels (1 x 10 (exp -4) M to 1 x 10 (exp -5) M) were added to the sol. The group IV Pc's, SnPc(OSi(n-hexyl)3)2 and GePc(OSi(n-hexyl)3)2, are insoluble in water and the process was changed accordingly. In these cases, the compounds were dissolved in THF and then added to the sol. The Pc concentration in the sol was 2 x 10(exp -5)M. The samples were then aged and dried in the standard method of making xerogel monoliths. Comparative nanosecond optical limiting experiments were performed on silica xerogels that were doped with the different metallophthalocyanines. The ratio of the net excited state absorption cross section (sigma(sub e)) to the ground state cross section (sigma(sub g)) is an important figure of merit that is used to characterize these materials. By this standard the SnPc sample exhibits the best limiting for the Pc doped sol-gel materials. Its cross section ratio of 19 compares favorably with the value of 22 that was measured in toluene. The GePc materials appear to not be as useful as those containing SnPc. The GePc doped solids exhibit a higher onset energy (2.5 mj and lower cross section ratio, 7. The CuPc4S sol-gel material has a still lower cross section ratio, 4, however, the tetrasulfonate groups make the dye soluble in water which greatly facilitates its incorporation into the sol-gel matrix. The nonlinear transmission of CuPc4S in a pH 2 buffer solution and in a silica xerogel were compared. It is evident that the CuPc4S preserves its optical limiting behavior in the sol-gel matrix, indicating that the fundamental excited state absorption process is essentially the same for a molecule in solution or in the solid state. Although the spectroscopic details of energy level lifetimes are unknown, the significance is that passive optical limiting has been achieved in the solid state via incorporation of a dye into an inorganic host. The only compromise occurs at the extremely high energy regime where photobleaching is observed. This is a result of the limited mobility of the dye molecules in the solid silica host relative to a liquid host. The effects of photodegradation in the xerogel are additive, whereas the solution provides a supply of fresh molecules that are free to enter the active volume between pulses.

Graphene wrapped Copper Phthalocyanine nanotube: Enhanced photocatalytic activity for industrial waste water treatment

NASA Astrophysics Data System (ADS)

Mukherjee, Moumita; Ghorai, Uttam Kumar; Samanta, Madhupriya; Santra, Angshuman; Das, Gour P.; Chattopadhyay, Kalyan K.

2017-10-01

To improve the photocatalytic performance of metal phthalocyanine based catalyst, Copper Phthalocyanine (CuPc) functionalized reduced graphene oxide (RGO) nanocomposite has been synthesized through a simple chemical approach. The obtained product was characterized by X-ray diffraction technique (XRD), Fourier transform infrared (FTIR) spectroscopy, Ultraviolet-visible spectroscopy (UV-vis) and High resolution transmission electron microscopy (HRTEM). The photocatalytic activity of the RGO/CuPc nanocomposite was performed by the degradation of Rhodamine B (RhB) under visible light irradiation. The photocatalytic studies revealed that the RGO/CuPc nanocomposite exhibits much stronger catalytic behavior than the pristine CuPc nanotube. A plausible mechanism for the photodegradation of Rhodamine B (RhB) was suggested. The RGO wrapped CuPc nanotube composite materials offer great potential as active photocatalysts for degradation of organic pollutions in industrial waste water.

Method of solubilizing phthalocyanines and metallophthalocyanines

DOEpatents

Rathke, Jerome W.; Chen, Michael J.; Fendrick, Carol M.

1997-11-04

A one-step method of manufacturing soluble phthalocyanines and metallophthalocyanines, like zinc phthalocyanine, by converting a phthalocyanine or a metallophthalocyanine to a trialkylsilyl-substituted derivative is disclosed. The phthalocyanine or metallophthalocyanine is converted to a soluble trialkylsilyl-substituted derivative by interacting the phthalocyanine or metallophthalocyanine with an active metal amide, like lithium 2,2,6,6-tetramethylpiperidide, and a halotrialkylsilane, like chlorotrimethylsilane, to provide a phthalocyanine compound, like phthalocyanine monomers, dimers or polymers, metalated or unmetalated, that are soluble in organic media.

Method of solubilizing phthalocyanines and metallophthalocyanines

DOEpatents

Rathke, Jerome W.; Chen, Michael J.; Fendrick, Carol M.

1997-01-01

A one-step method of manufacturing soluble phthalocyanines and metallophthalocyanines, like zinc phthalocyanine, by converting a phthalocyanine or a metallophthalocyanine to a trialkylsilyl-substituted derivative is disclosed. The phthalocyanine or metallophthalocyanine is converted to a soluble trialkylsilyl-substituted derivative by interacting the phthalocyanine or metallophthalocyanine with an active metal amide, like lithium 2,2,6,6-tetramethylpiperidide, and a halotrialkylsilane, like chlorotrimethylsilane, to provide a phthalocyanine compound, like phthalocyanine monomers, dimers or polymers, metalated or unmetalated, that are soluble in organic media.

Axially substituted silicon(IV) phthalocyanine and its quaternized derivative as photosensitizers towards tumor cells and bacterial pathogens.

PubMed

Ömeroğlu, İpek; Kaya, Esra Nur; Göksel, Meltem; Kussovski, Vesselin; Mantareva, Vanya; Durmuş, Mahmut

2017-10-15

Axially di-(alpha,alpha-diphenyl-4-pyridylmethoxy) silicon(IV) phthalocyanine (3) and its quaternized derivative (3Q) were synthesized and tested as photosensitizers against tumor and bacterial cells. These new phthalocyanines were characterized by elemental analysis, and different spectroscopic methods such as FT-IR, UV-Vis, MALDI-TOF and 1 H NMR. The photophysical properties such as absorption and fluorescence, and the photochemical properties such as singlet oxygen generation of both phthalocyanines were investigated in solutions. The obtained values were compared to the values obtained with unsubstituted silicon(IV) phthalocyanine dichloride (SiPcCl 2 ). The addition of two di-(alpha,alpha-diphenyl-4-pyridylmethanol) groups as axial ligands showed an improvement of the photophysical and photochemical properties and an increasement of the singlet oxygen quantum yield (Φ Δ ) from 0.15 to 0.33 was determined. The photodynamic efficacy of synthesized photosensitizers (3 and 3Q) were evaluated with promising photocytotoxicity (17% cell survival for 3 and 28% for 3Q) against the cervical cancer cell line (HeLa). The photodynamic inactivation of pathogenic bacterial strains Streptococcus mutans, Staphylococcus aureus, and Pseudomonas aeruginosa suggested a high susceptibility with quaternized derivative (3Q). The both Gram-positive bacterial strains were fully photoinactivated with 11μM 3Q and mild light dose 50J.cm -2 . In case of P. aeruginosa the effect was negligible for concentrations up to 22μM 3Q and light dose 100J.cm -2 . The results suggested that the novel axially substituted silicon(IV) phthalocyanines have promising characteristic as photosensitizer towards tumor cells. The quaternized derivative 3Q has high potential for photoinactivation of pathogenic bacterial species. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrochemical and spectroelectrochemical study on novel non-peripherally tetra 1,2,4-triazole substituted phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akyüz, Duygu; Akçay, Hakkı Türker; Koca, Atıf; Bekircan, Olcay; Kantekin, Halit

2018-03-01

In the present study novel tetra 4-(4-fluorophenyl)-5-(4-methoxyphenyl)-4H-1,2,4-triazole-3-thio substituted non-peripherally metal free (4), zinc(II) (5), lead (II) (6) and copper(II) (7) phthalocyanines were synthesized. The obtained novel compounds were characterized by a combination of FT-IR, 1H NMR, UV-Vis and MALDI-TOF techniques. The redox properties of the complexes have been investigated via cyclic voltammetry, square wave voltammetry and in situ spectroelectrochemistry. The compounds displayed ring-based, reversible and/or quasi-reversible reduction and oxidation processes and aggregation of the complexes influenced the redox character of the processes. The color changes during the redox processes of metallo phthalocyanine were recorded by in-situ spectroelectrochemical measurements. In situ UV-vis spectroelectrochemical measurements, which was associated with color change of the complexes, showed their applicability in the fields of the electrochemical technologies.

Phthalocyanine Doped Metal Oxide Nanoparticles on Multiwalled Carbon Nanotubes Platform for the detection of Dopamine

NASA Astrophysics Data System (ADS)

Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Fayemi, Omolola E.; Olasunkanmi, Lukman O.; Ebenso, Eno E.

2017-03-01

The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ.

Phthalocyanine Doped Metal Oxide Nanoparticles on Multiwalled Carbon Nanotubes Platform for the detection of Dopamine

PubMed Central

Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Fayemi, Omolola E.; Olasunkanmi, Lukman O.; Ebenso, Eno E.

2017-01-01

The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ. PMID:28256521

Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films.

PubMed

Chickneyan, Zarui Sara; Briseno, Alejandro L; Shi, Xiangyang; Han, Shubo; Huang, Jiaxing; Zhou, Feimeng

2004-07-01

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.

Immobilization of zinc phthalocyanines in silicate matrices and investigation of their photobactericidal effect on E. coli.

PubMed

Artarsky, Spas; Dimitrova, Stanislava; Bonnett, Raymond; Krysteva, Milka

2006-03-26

The aim of the present investigation was to immobilize zinc phthalocyanines in a silicate matrix and to test the photobactericidal properties of the matrices so prepared toward Esherichia coli in model aqueous media. For the purpose, tetra tertiary butyl zinc phthalocyanine (TBZnPc) and zinc phthalocyanine tetrasulfonic acid (ZnPcTS) were used. The abilities of these two photosensitizers to generate singlet oxygen in solution were compared by following the rate of photobleaching of 1,3-diphenylisobenzofuran (DPBF) at 430 nm in dimethylformamide (DMF). The results of this study show clearly that, under the conditions used here, the TBZnPc is the more effective generator of singlet oxygen; with it the DPBF was virtually completely photobleached in 4 min, while with the ZnPcTS under the same conditions, it took 12 min to reach this point. Glass conjugates with the two phthalocyanines were obtained by the sol-gel technique and were characterized by a well-defined color due to the phthalocyanine incorporated in the silicate matrix. Glasses with an intense, but inhomogeneous, green color were obtained when the tetrasulfonic derivative of the zinc phthalocyanine was used, while blue glasses of evenly distributed coloration were formed from the tetra tertiary butyl derivative. The ZnPcTS conjugate demonstrates more effective singlet oxygen evolution than is the case with the TBZnPc conjugate. These results are the opposite of those obtained for the free phthalocyanines in solution. The structural formulae of the compounds show that TBZnPc has a more pronounced hydrophobic character than the sulfonic derivative. In our view, the relative reactivities of the conjugates can be explained by the tetrasulfonic derivative being situated mainly in the surface parts of the glass matrix where the hydrophilic character is prevailing, while the tertiary butyl derivative is mainly present in the internal parts of the matrix as a result of which it is less accessible and therefore less active. The results obtained on the effect of zinc phthalocyanine conjugates on E. coli show a trend similar to that observed with singlet oxygen evolution shown. Thus, for the ZnPcTS conjugate, the log kill is 1.32 and for the TBZnPc conjugate, it is 0.98, in each case after 120 min. The results obtained show that phthalocyanines can be immobilized successfully in a silicate matrix and used for photodisinfection of microbially polluted waters. The silicate matrix has some advantages in comparison with other organic matrices. It is insoluble in water, resistant towards microorganisms, easy to fabricate, and might be developed successfully for the photodisinfection of water, e.g., in swimming pools and in other open water reservoirs.

Intramolecular aggregation and optical limiting properties of triazine-linked mono-, bis- and tris-phthalocyanines.

PubMed

Chen, Jun; Zhang, Tao; Wang, Shuangqing; Hu, Rui; Li, Shayu; Ma, Jin Shi; Yang, Guoqiang

2015-10-05

A series of triazine-linked mono-, bis- and tris-phthalocyanines are synthesized, intramolecular aggregation is found in bis- and tris-phthalocyanines via π-π stacking interaction. Theoretical and experimental studies reveal the formation of the intramolecular aggregation. The spectrographic, photophysical and nonlinear optical properties of these compounds are adjusted for the formation of the intramolecular aggregation. The bis-phthalocyanine dimer presents smaller fluorescence quantum yield, lower triplet formation yield and the triplet-minus-ground state extinction coefficient, which causes poorer optical limiting performance. It is interesting that the tris-phthalocyanine is composed of a mono-phthalocyanine part and a bis-phthalocyanine part, the optical limiting property of the tris-phthalocyanine is similar to that of mono-phthalocyanine. Copyright © 2015 Elsevier B.V. All rights reserved.

Probing the Dipolar Coupling in a Heterospin Endohedral Fullerene-Phthalocyanine Dyad.

PubMed

Zhou, Shen; Yamamoto, Masanori; Briggs, G Andrew D; Imahori, Hiroshi; Porfyrakis, Kyriakos

2016-02-03

Paramagnetic endohedral fullerenes and phthalocyanine (Pc) complexes are promising building blocks for molecular quantum information processing, for which tunable dipolar coupling is required. We have linked these two spin qubit candidates together and characterized the resulting electron paramagnetic resonance properties, including the spin dipolar coupling between the fullerene spin and the copper spin. Having interpreted the distance-dependent coupling strength quantitatively and further discussed the antiferromagnetic aggregation effect of the CuPc moieties, we demonstrate two ways of tuning the dipolar coupling in such dyad systems: changing the spacer group and adjusting the solution concentration.

Antimicrobial photodisinfection with Zn(II) phthalocyanine adsorbed on TiO2 upon UVA and red irradiation

NASA Astrophysics Data System (ADS)

Mantareva, Vanya; Eneva, Ivelina; Kussovski, Vesselin; Borisova, Ekaterina; Angelov, Ivan

2015-01-01

The light exposure on a daily basis has been well accepted as a competitive method for decontamination of wastewater. The catalytic properties of TiO2 offer a great potential to reduce the transmission of pathogens in the environment. Although the titanium dioxide shows high activity against pathogens, its general usage in water cleaning is limited due to the insufficient excitation natural light (about 3% of the solar spectrum). A hydrophobic dodecylpyridyloxy Zn(II)-phthalocyanine with four peripheral hydrocarbon chains of C12 (ZnPcDo) was immobilized on a photocatalyst TiO2 anatase (P25). The resulted greenish colored nanoparticles of phthalocyanine were characterized by the means of absorption, fluorescence and infrared spectroscopy. The laser scanning confocal fluorescence microscopy was used to visualize the phthalocyanine dye by the red fluorescence emission (650 - 740 nm). The intensive Q-band in the far red visible spectral region (~ 690 nm) suggested a monomeric state of phthalocyanine on TiO2 nanoparticles. Two pathogenic bacterial strains (methicillin-resistant Staphylococcus aureus - MRSA and Salmonella enteritidis) associated with wastewater were photoinactivated with the suspension of the particles. The effective photoinactivation was observed with 1 g.L-1 TiO2 anatase at irradiation with UVA 364 nm as with UVA 364 nm and LED 643 nm. The gram-negative Salmonella enteritidis was fully photoinactivated with ZnPcDo-TiO2 and TiO2 alone at UVA 346 nm and at irradiation with two light sources (364 nm + 643 nm). The proposed conjugate appears as an useful composite material for antibacterial disinfection.

Mono-Amine Functionalized Phthalocyanines: Mwave-Assisted Solid-Phase Synthesis and Bioconjugation Strategies

PubMed Central

Erdem, S. Sibel; Nesterova, Irina V.; Soper, Steven A.; Hammer, Robert P.

2009-01-01

Phthalocyanines (Pcs) are excellent candidates for use as fluors for near-infrared (near-IR) fluorescent tagging of biomolecules for a wide variety of bioanalytical applications. Mono-functionalized Pcs, having two different types of peripheral substitutents; one for covalent conjugation of the Pc to biomolecules and others to improve the solubility of the macrocycle, ideally suit for the desired applications. To date, difficulties faced during the purification of the mono-functionalized Pcs limited their usage in various types of applications. Herein are reported a new synthetic method for rapid synthesis of the target Pcs and bioconjugation techniques for labeling of the oligonucleotides with the near-IR flours. A novel synthetic route was developed utilizing a hydrophilic, polyethylene glycol-based (PEG) support with an acid labile Rink Amide linker. The Pcs were functionalized with an amine group for covalent conjugation purposes and were decorated with short PEG chains, serving as solubilizing groups. Mwave-assisted solid-phase synthetic method was successfully applied to obtain pure asymmetrically-substituted mono-amine functionalized Pcs in a short period of time. Three different bioconjugation techniques, reductive amination, amidation and Huisgen cycloaddition, were employed for covalent conjugation of Pcs to oligonucleotides. The described μwave-assisted bioconjugation methods give an opportunity to synthesize and isolate the Pc-oligonucleotide conjugate in a few hours. PMID:19911767

Structural and magnetic characterization of copper sulfonated phthalocyanine grafted onto treated polyethylene

NASA Astrophysics Data System (ADS)

Reznickova, A.; Kolska, Z.; Orendac, M.; Cizmar, E.; Sajdl, P.; Svorcik, V.

2016-08-01

This study focuses on high density polyethylene (HDPE) activated by Ar plasma treatment, subsequently grafted with copper sulfonated phthalocyanine (CuPc) especially pointing out to the surface and magnetic properties of those composites. Properties of pristine PE and their plasma treated counterparts were studied by different experimental techniques: X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, zeta potential and by electron spin resonance (ESR). XPS analysis confirmed the successful grafting of phthalocyanine. The highest absorption was found for the sample grafted with bCuPc for 1 h. Electrokinetic analysis also confirmed the plasma treatment and also subsequent CuPc grafting influence significantly the surface chemistry and charge. These results correspond well with XPS determination. ESR studies confirmed the presence of CuPc grafted on HDPE. It was found, that grafting is mediated by magnetically inactive functional groups, rather than radicals. Magnetic properties of CuPc do not seem to change significantly after grafting CuPc on polyethylene surface.

Unexpected Rotamerism at the Origin of a Chessboard Supramolecular Assembly of Ruthenium Phthalocyanine.

PubMed

Mattioli, Giuseppe; Larciprete, Rosanna; Alippi, Paola; Bonapasta, Aldo Amore; Filippone, Francesco; Lacovig, Paolo; Lizzit, Silvano; Paoletti, Anna Maria; Pennesi, Giovanna; Ronci, Fabio; Zanotti, Gloria; Colonna, Stefano

2017-11-16

We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc) 2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru-Ru bond, (RuPc) 2 can be found in two stable rotameric forms separated by a low-energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard-like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π-stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc) 2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanostructuring on zinc phthalocyanine thin films for single-junction organic solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaudhary, Dhirendra K.; Kumar, Lokendra, E-mail: lokendrakr@allduniv.ac.in

2016-05-23

Vertically aligned and random oriented crystalline molecular nanorods of organic semiconducting Zinc Phthalocyanine (ZnPc) have been grown on ITO coated glass substrate using solvent volatilization method. Interesting changes in surface morphology were observed under different solvent treatment. Vertically aligned nanorods of ZnPc thin film were observed in the films treated with acetone, where as the random oriented nanorods were observed in the films treated with chloroform. The X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) have been used for characterization of nanostructures. The optical properties of the nanorods have been investigated by UV-Vis. absorption spectroscopy.

Photodynamic therapy potential of thiol-stabilized CdTe quantum dot-group 3A phthalocyanine conjugates (QD-Pc).

PubMed

Tekdaş, Duygu Aydın; Durmuş, Mahmut; Yanık, Hülya; Ahsen, Vefa

2012-07-01

Thiol stabilized CdTe quantum dot (QD) nanoparticles were synthesized in aqueous phase and were used as energy donors to tetra-triethyleneoxythia substituted aluminum, gallium and indium phthalocyanines through fluorescence resonance energy transfer (FRET). Energy transfer occurred from the QDs to phthalocyanines upon photoexcitation of the QDs. An enhancement in efficiency of energy transfer with the nature of the carboxylic thiol stabilizer on the QDs was observed. As a result of the nanoparticle and the phthalocyanine mixing, the photoluminescence efficiency of the phthalocyanine moieties in the mixtures does not strictly follow the quantum yields of the bare phthalocyanines. The photochemistry study of phthalocyanines in the presence of the QDs revealed high singlet oxygen quantum yield, hence the possibility of using QDs in combination with phthalocyanines as photosensitizers in photodynamic therapy of cancer. The fluorescence of the CdTe quantum dots-phthalocyanine conjugates (QDs-Pc) were effectively quenched by addition of 1,4-benzoquinone. Copyright © 2012 Elsevier B.V. All rights reserved.

DNA-binding and oxidative properties of cationic phthalocyanines and their dimeric complexes with anionic phthalocyanines covalently linked to oligonucleotides.

PubMed

Kuznetsova, A A; Lukyanets, E A; Solovyeva, L I; Knorre, D G; Fedorova, O S

2008-12-01

Design of chemically modified oligonucleotides for regulation of gene expression has attracted considerable attention over the past decades. One actively pursued approach involves antisense or antigene oligonucleotide constructs carrying reactive groups, many of these based on transition metal complexes. The complexes of Fe(II) and Co(II) with phthalocyanines are extremely good catalysts of oxidation of organic compounds with molecular oxygen and hydrogen peroxide. The binding of positively charged Fe(II) and Co(II) phthalocyanines with single- and double-stranded DNA was investigated. It was shown that these phthalocyanines interact with nucleic acids through an outside binding mode. The site-directed modification of single-stranded DNA by O2 and H2O2 in the presence of dimeric complexes of negatively and positively charged Fe(II) and Co(II) phthalocyanines was investigated. These complexes were formed directly on single-stranded DNA through interaction between negatively charged phthalocyanine in conjugate and positively charged phthalocyanine in solution. The resulting oppositely charged phthalocyanine complexes showed significant increase of catalytic activity compared with monomeric forms of phthalocyanines Fe(II) and Co(II). These complexes catalyzed the DNA oxidation with high efficacy and led to direct DNA strand cleavage. It was determined that oxidation of DNA by molecular oxygen catalyzed by complex of Fe(II)-phthalocyanines proceeds with higher rate than in the case of Co(II)-phthalocyanines but the latter led to a greater extent of target DNA modification.

Boron-containing chlorins and tetraazaporphyrins: synthesis and cell uptake of boronated pyropheophorbide a derivatives.

PubMed

Ratajski, Michal; Osterloh, Jens; Gabel, Detlef

2006-03-01

The literature on the synthesis and the biological properties of boron-containing chlorins and phthalocyanines is reviewed. A series of homologous derivatives of pyropheophorbide A is described. The compounds contain the B(12)H(11)SH(2-) cluster attached to the single carboxyl group and vary in the length of the alkyl chain (methyl, propyl, pentyl, heptyl and nonyl) attached via an ether linkage to the former vinyl group. Cellular uptake was found for all derivatives except the nonyl sidechain. The compounds were moderately cell-toxic. Localization in lysosomes could be excluded; the compounds localized probably in the mitochondria.

The use of phthalocyanines in cancer therapy

NASA Astrophysics Data System (ADS)

Nyokong, Tebello; Gledhill, Igle

2013-03-01

Phthalocyanines are synthetic analogues of porphyrins employed as photosensitizers in cancer therapy. We present the history of photodynamic therapy and developments in the use of phthalocyanines as photosensitizers. New efforts in the development of more cancer-specific phthalocyanines are presented. The combination of phthalocyanines with nanoparticles for "combination therapy" of cancer is also discussed. The nanoparticles employed are quantum dots, gold, and magnetic nanoparticles.

Comparison of interaction mechanisms of copper phthalocyanine and nickel phthalocyanine thin films with chemical vapours

NASA Astrophysics Data System (ADS)

Ridhi, R.; Singh, Sukhdeep; Saini, G. S. S.; Tripathi, S. K.

2018-04-01

The present study deals with comparing interaction mechanisms of copper phthalocyanine and nickel phthalocyanine with versatile chemical vapours: reducing, stable aromatic and oxidizing vapours namely; diethylamine, benzene and bromine. The variation in electrical current of phthalocyanines with exposure of chemical vapours is used as the detection parameter for studying interaction behaviour. Nickel phthalocyanine is found to exhibit anomalous behaviour after exposure of reducing vapour diethylamine due to alteration in its spectroscopic transitions and magnetic states. The observed sensitivities of copper phthalocyanine and nickel phthalcyanine films are different in spite of their similar bond numbers, indicating significant role of central metal atom in interaction mechanism. The variations in electronic transition levels after vapours exposure, studied using UV-Visible spectroscopy confirmed our electrical sensing results. Bromine exposure leads to significant changes in vibrational bands of metal phthalocyanines as compared to other vapours.

Adsorption and Wetting in Model Mesoporous Silicas and in Complex Metal Oxide Catalysts

NASA Astrophysics Data System (ADS)

Jayaraman, Karthik

The surface of most metal oxides is covered by hydroxyl groups which influence many surface phenomena such as adsorption and wetting, catalysis and surface reactions. Surface chemistry of silica is a subject of exhaustive studies owing to a wide variety of practical applications of silica. In Chapter 1, a brief review of classification, synthesis and characterization of silica is provided. The hydroxylation of silica surface i.e the number of hydroxyl (-OH) groups on the surface is of utmost importance for its practical applications. In Chapter 2, a brief introduction to surface hydration of silica is provided followed by the gas adsorption measurements and characterization. Pore wetting is critical to many applications of mesoporous adsorbents, catalysts, and separation materials. In the work presented in Chapter 3, we employed the combined vapor adsorption study using nitrogen (77K) and water (293K) isotherms to evaluate the water contact angles for a series of ordered mesoporous silicas (ex:SBA-15). The proposed method of contact angle relies on the statistical film thickness (t-curve) of the adsorbed water. There were no t-curves for water for dehydroxylated or hydrophobic surfaces in literature and we addressed this issue by measuring t-curves for a series of model surfaces with known and varying silanol coverage. Using the radius of menisci ((H2O)), statistical film thickness t(H2O) from water isotherm, and the true radius of pores (rp(N 2)), from nitrogen isotherms, the water contact angle inside pores were calculated. As it was anticipated, the results obtained showed that the silica pore contact angles were strongly influenced by the number of the surface silanol groups and, therefore, by the thermal and hydration treatments of silicas. Phthalocyanines (Pcs) present an interesting class of catalytically active of molecules with unique spectroscopic, photoelectric, and sometimes magnetic properties. In the work presented in Chapter 4, we have undertaken a systematic study to explore the possibility of preparing a supported catalyst material i.e loading fluorinated metal phthalocyanines onto metal oxide surfaces by two other techniques in addition to solution adsorption. Techniques or procedures that have been used to immobilize MPcs include: i) physical adsorption (from solution) onto metal oxide surface, ii) deposition by pore filling and encapsulation and iii) mesopore entrapment or confinement. The MPcs are loaded on to metal oxides with an aim to: a) maximize the surface area of the Pcs by distributing it over the support, b) immobilize the Pcs so that they do not leach into the solution environment, c) improve the thermal stability of the Pcs and d) attempt to achieve single-site catalysis. All the immobilization techniques were carried out with F64PcZn as the model MPc, acetone as the immobilization solvent and silica or alumina as adsorbents (solid support). An understanding of gas adsorption mechanisms on metal phthalocyanines (MPcs) is essential for their practical application in biological processes, gas sensing, and catalysis. In this work, the surface characteristics were probed by performing nitrogen and water adsorption on the free-form MPcs (without immobilization on solid support) and characterization of their physical properties. The combined vapor adsorption study (developed in Chapter 3) enabled in understanding the affinity of Pcs towards water vapor i.e number of water molecules adsorbed per phthalocyanine molecule was obtained. This information is very relevant towards using Pcs as catalyst since water vapor is guaranteed to be present in most of the catalytic reaction environment.

Effect of diode-laser and AC magnetic field of bovine serum albumin nanospheres loaded with phthalocyanine and magnetic particles.

PubMed

Simioni, Andreza Ribeiro; Rodrigues, Marcilene M A; Primo, Fernando L; Morais, Paulo C; Tedesco, Antonio Claudio

2011-04-01

This study reports on the development and characterization of bovine serum albumin (BSA) nanospheres containing Silicon(IV) phthalocyanine (NzPc) and/or maghemite nanoparticles (MNP), the latter introduced via ionic magnetic fluid (MF). The nanosized BSA-loaded samples were designed for synergic application while combining Photodynamic Therapy and Hyperthermia. Incorporation of MNP in the albumin-based template, allowing full control of the magnetic content, was accomplished by adding a highly-stable ionic magnetic fluid sample to the albumin suspension, following heat denaturing. The material's evaluation was performed using Zeta potential measurements and scanning electron microscopy. The samples were characterized by steady-state techniques and time-resolved fluorescence. The in vitro assay, using human fibroblasts, revealed no cytotoxic effect in all samples investigated, demonstrating the potential of the tested system as a synergistic drug delivery system.

Preparation and sonodynamic activities of water-soluble tetra-α-(3-carboxyphenoxyl) zinc(II) phthalocyanine and its bovine serum albumin conjugate.

PubMed

Xu, He-Nan; Chen, Hai-Jun; Zheng, Bi-Yuan; Zheng, Yun-Quan; Ke, Mei-Rong; Huang, Jian-Dong

2015-01-01

Sonodynamic therapy (SDT) is a new approach for cancer treatment, involving the synergistic effect of ultrasound and certain chemical compounds termed as sonosensitizers. A water-soluble phthalocyanine, namely tetra-α-(3-carboxyphenoxyl) zinc(II) phthalocyanine (ZnPcC4), has been prepared and characterized. The interactions between ZnPcC4 and bovine serum albumin (BSA) were also investigated by absorption and fluorescence spectroscopy. It was found that there were strong interactions between ZnPcC4 and BSA with a binding constant of 6.83×10(7)M(-1). A non-covalent BSA conjugate of ZnPcC4 (ZnPcC4-BSA) was prepared. Both ZnPcC4 and ZnPcC4-BSA exhibited efficient sonodynamic activities against HepG2 human hepatocarcinoma cells. Compared with ZnPcC4, conjugate ZnPcC4-BSA showed a higher sonodynamic activity with an IC50 value of 7.5μM. Upon illumination with ultrasound, ZnPcC4-BSA can induce an increase of intracellular reactive oxygen species (ROS) level, resulting in cellular apoptosis. The results suggest that the albumin conjugates of zinc(II) phthalocyanines functionalized with carboxyls can serve as promising sonosensitizers for sonodynamic therapy. Copyright © 2014 Elsevier B.V. All rights reserved.

Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol

NASA Astrophysics Data System (ADS)

Makinde, Zainab O.; Louzada, Marcel; Mashazi, Philani; Nyokong, Tebello; Khene, Samson

2017-12-01

Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.

Mono- and tetra-substituted zinc(II) phthalocyanines containing morpholinyl moieties: Synthesis, antifungal photodynamic activities, and structure-activity relationships.

PubMed

Zheng, Bi-Yuan; Ke, Mei-Rong; Lan, Wen-Liang; Hou, Lu; Guo, Jun; Wan, Dong-Hua; Cheong, Ling-Zhi; Huang, Jian-Dong

2016-05-23

A series of zinc(II) phthalocyanines (ZnPcs) mono-substituted and tetra-substituted with morpholinyl moieties and their quaternized derivatives have been synthesized and evaluated for their antifungal photodynamic activities toward Candida albicans. The α-substituted, quaternized, and mono-substituted ZnPcs are found to have higher antifungal photoactivity than β-substituted, neutral, and tetra-substituted counterparts. The cationic α-mono-substituted ZnPc (6a) exhibits the highest photocytotoxicity. Moreover, it is more potent than axially di-substituted analogue. The different photocytotoxicities of these compounds have also been rationalized by investigating their spectroscopic and photochemical properties, aggregation trend, partition coefficients, and cellular uptake. The IC90 value of 6a against C. albicans cells is as low as 3.3 μM with a light dose of 27 J cm(-2), meaning that 6a is a promising candidate as the antifungal photosensitizer for future investigations. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

METAL PHTHALOCYANINES

DOEpatents

Frigerio, N.A.

1962-03-27

A process is given for preparing heavy metal phthalocyanines, sulfonated or not. The process comprises mixing an inorganic metal salt with dimethyl formamide or methyl sulfoxide; separating the metal complex formed from the solution; mixing the complex with an equimolar amount of sodium, potassium, lithium, magnesium, or beryllium sulfonated or unsulfonated phthalocyanine whereby heavy-metal phthalocyanine crystals are formed; and separating the crystals from the solution. Uranyl, thorium, lead, hafnium, and lanthanide rare earth phthalocyanines can be produced by the process. (AEC)

[Photophysical properties and photodynamic activity of nanostructured aluminium phthalocyanines].

PubMed

Udartseva, O O; Lobanov, A V; Andeeva, E R; Dmitrieva, G S; Mel'nikov, M Ia; Buravkova, L B

2014-01-01

We developed water-soluble supramolecular complexes of aluminium phthalocyanine based on mesoporous silica nanoparticles and polyvinylpirrolidone containing rare photoactive nanoaggregates. Radiative lifetimes, extinction coefficients and energy of electronic transitions of isolated and associated metal phthalocyanine complexes were calculated. Nontoxic concentrations of synthesized nanocomposite photosensibilizers were in vitro determined. In present study we compared photodynamic treatment efficacy using different modifications of aluminium phthalocyanine (Photosens®, AlPc-nSiO2 and AlPc-PVP). Mesenchymal stromal cells were used as a model for photodynamic treatment. Intracellular accumulation of aluminium phthalocyanine based on mesoporous silica nanoparticles AlPc-nSiO2 was the most efficient. Illumination of phthalocyanine-loaded cells led to reactive oxygen species generation and subsequent apoptotic cell death. Silica nanoparticles provided a significant decrease of effective phthalocyanine concentration and enhanced cytotoxicity of photodynamic treatment.

40 CFR 721.9674 - Sulfonated-copper phthalocyanine salt of a triarylmethane dye (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Sulfonated-copper phthalocyanine salt... Significant New Uses for Specific Chemical Substances § 721.9674 Sulfonated-copper phthalocyanine salt of a... chemical substance identified generically as sulfonated-copper phthalocyanine salt of a triarylmethane dye...

40 CFR 721.9674 - Sulfonated-copper phthalocyanine salt of a triarylmethane dye (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Sulfonated-copper phthalocyanine salt... Significant New Uses for Specific Chemical Substances § 721.9674 Sulfonated-copper phthalocyanine salt of a... chemical substance identified generically as sulfonated-copper phthalocyanine salt of a triarylmethane dye...

40 CFR 721.9674 - Sulfonated-copper phthalocyanine salt of a triarylmethane dye (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Sulfonated-copper phthalocyanine salt... Significant New Uses for Specific Chemical Substances § 721.9674 Sulfonated-copper phthalocyanine salt of a... chemical substance identified generically as sulfonated-copper phthalocyanine salt of a triarylmethane dye...

21 CFR 73.3124 - Phthalocyanine green.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Phthalocyanine green. 73.3124 Section 73.3124 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3124 Phthalocyanine green. (a) Identity. The color additive is phthalocyanine green (CAS Reg. No. 1328-53-6), Colour Index No. 74260. (b) Uses...

21 CFR 73.3124 - Phthalocyanine green.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Phthalocyanine green. 73.3124 Section 73.3124 Food... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3124 Phthalocyanine green. (a) Identity. The color additive is phthalocyanine green (CAS Reg. No. 1328-53-6), Colour Index No. 74260. (b) Uses...

40 CFR 721.9674 - Sulfonated-copper phthalocyanine salt of a triarylmethane dye (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Sulfonated-copper phthalocyanine salt... Significant New Uses for Specific Chemical Substances § 721.9674 Sulfonated-copper phthalocyanine salt of a... chemical substance identified generically as sulfonated-copper phthalocyanine salt of a triarylmethane dye...

40 CFR 721.9674 - Sulfonated-copper phthalocyanine salt of a triarylmethane dye (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Sulfonated-copper phthalocyanine salt... Significant New Uses for Specific Chemical Substances § 721.9674 Sulfonated-copper phthalocyanine salt of a... chemical substance identified generically as sulfonated-copper phthalocyanine salt of a triarylmethane dye...

Layer-by-layer composite film of nickel phthalocyanine and montmorillonite clay for synergistic effect on electrochemical detection of dopamine

NASA Astrophysics Data System (ADS)

de Lucena, Nathalia C.; Miyazaki, Celina M.; Shimizu, Flávio M.; Constantino, Carlos J. L.; Ferreira, Marystela

2018-04-01

Dopamine (DA) abnormal levels are related to diseases which makes important the development of fast, reliable, low-cost and sensitive devices for diagnosis and pharmaceutical controls. Nanostructured film composite of sodium montmorillonite clay (Na+MMT) and nickel phthalocyanine (NiTsPc) was self-assembled by layer-by-layer (LbL) technique and applied as electrochemical sensor for DA in the presence of common natural interferents as ascorbic acid (AA) and uric acid (UA). Three different LbL architecture films were investigated: LbL films of clay (PEI/Na+MMT) and phthalocyanine (PEI/NiTsPc) in a bilayer structure with a conventional polyelectrolyte (PEI) and a composite film formed by both materials to verify the synergistic effect in the LbL film in a quadri-layer assembly (PEI/Na+MMT/PEI/NiTsPc). Structural characterization indicated molecular level interactions between the layers forming the LbL films. The ITO/(PEI/Na+MMT/PEI/NiTsPc)10 electrode exhibited a LOD of 1.0 μmol L-1 and linear range 5-150 μmol L-1.

Investigations and application in piezoelectric phenol sensor of Langmuir-Schäfer films of a copper phthalocyanine derivative functionalized with bulky substituents.

PubMed

Giancane, G; Basova, T; Hassan, A; Gümüş, G; Gürek, A G; Ahsen, V; Valli, L

2012-07-01

An octa-substituted copper phthalocyanine was dissolved in chloroform and spread on ultrapure water subphase in a Langmuir trough. The floating films were characterized at the air-water interface by the Langmuir isotherm, Brewster angle microscopy, and UV-Vis reflection spectroscopy and transferred by Langmuir-Schäfer technique on a silicon substrate, and thickness, refractive index, and extinction coefficient of the phthalocyanine derivative thin film were calculated by means of spectroscopic ellipsometry. A different number of layers were deposited using Langmuir-Schäfer method onto QCM crystals, and the active layers were tested as sensors for the detection of phenols in aqueous solution. The piezoelectric sensor response, totally reversible, is influenced by the number of transferred layers and by the nature of the substituent; on the contrary, the pK(a) value of the injected analytes slightly affects the device performances. Repeatability of the sensor responses was tested, and the frequency variation appears unchanged at least for 100 days. Copyright © 2012 Elsevier Inc. All rights reserved.

Active site formation mechanism of carbon-based oxygen reduction catalysts derived from a hyperbranched iron phthalocyanine polymer.

PubMed

Hiraike, Yusuke; Saito, Makoto; Niwa, Hideharu; Kobayashi, Masaki; Harada, Yoshihisa; Oshima, Masaharu; Kim, Jaehong; Nabae, Yuta; Kakimoto, Masa-Aki

2015-01-01

Carbon-based cathode catalysts derived from a hyperbranched iron phthalocyanine polymer (HB-FePc) were characterized, and their active-site formation mechanism was studied by synchrotron-based spectroscopy. The properties of the HB-FePc catalyst are compared with those of a catalyst with high oxygen reduction reaction (ORR) activity synthesized from a mixture of iron phthalocyanine and phenolic resin (FePc/PhRs). Electrochemical measurements demonstrate that the HB-FePc catalyst does not lose its ORR activity up to 900°C, whereas that of the FePc/PhRs catalyst decreases above 700°C. Hard X-ray photoemission spectra reveal that the HB-FePc catalysts retain more nitrogen components than the FePc/PhRs catalysts between pyrolysis temperatures of 600°C and 800°C. This is because the linked structure of the HB-FePc precursor has high thermostability against nitrogen desorption. Consequently, effective doping of active nitrogen species into the sp (2) carbon network of the HB-FePc catalysts may occur up to 900°C.

Ferrocenyl Phthalocyanine as Donor in Non-Poly(3-hexylthiophen-2,5-diyl) Bulk Heterojunction Solar Cell.

PubMed

Nar, Ilgın; Atsay, Armağan; Altındal, Ahmet; Hamuryudan, Esin; Koçak, Makbule B; Gül, Ahmet

2018-05-11

Bulk heterojunction (BHJ) solar cells might one day play a vital role in realizing low-cost and environmentally benign photovoltaic devices. In this work, a BHJ solar cell was designed, based on a hexadeca-substituted phthalocyanine (FcPc) with ferrocenyl linked to the phthalocyanine ring. Next, we sought to obtain more quantitative information about the usability of this newly synthesized compound as a donor material in BHJ solar cells. Thus, BHJs with the structure of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/FcPc:[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blend/LiF/Al were fabricated and characterized. The effect of blend ratio (0.5-2.0) on the BHJ solar cell parameters was also investigated. Interesting results were obtained in FcPc and the PCBM blend-based BHJ solar cell under optimized conditions. Our results presented here demonstrate that BHJ devices employing FcPc as a donor has great potential for the development of highly efficient non-poly(3-hexylthiophen-2,5-diyl) photovoltaic devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Room temperature ferromagnetism in a phthalocyanine based carbon material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Honda, Z., E-mail: honda@fms.saitama-u.ac.jp; Sato, K.; Sakai, M.

2014-02-07

We report on a simple method to fabricate a magnetic carbon material that contains nitrogen-coordinated transition metals and has a large magnetic moment. Highly chlorinated iron phthalocyanine was used as building blocks and potassium as a coupling reagent to uniformly disperse nitrogen-coordinated iron atoms on the phthalocyanine based carbon material. The iron phthalocyanine based carbon material exhibits ferromagnetic properties at room temperature and the ferromagnetic phase transition occurs at T{sub c} = 490 ± 10 K. Transmission electron microscopy observation, X-ray diffraction analysis, and the temperature dependence of magnetization suggest that the phthalocyanine molecules form three-dimensional random networks in the iron phthalocyanine based carbon material.

The Redox-Active Chromium Phthalocyanine System: Isolation of Five Oxidation States from Pc4- CrI to Pc2- CrIII.

PubMed

Zhou, Wen; Thompson, John R; Leznoff, Clifford C; Leznoff, Daniel B

2017-02-16

The preparation and structural characterization of a series of chromium phthalocyanine complexes with multiple metal and ring oxidation states were achieved using PcCr II (1) (Pc=phthalocyanine) or PcCr II (THF) 2 (1⋅THF 2 ) as starting materials. The reaction of soluble 1⋅THF 2 with Br 2 or I 2 gave the PcCr III halide complexes PcCrX(THF) (X=I/I 3 , Br; 3, 4, respectively). Treatment of 1 with 0.5 equivalent of PhIO or air generated the dinuclear [PcCr(THF)] 2 (μ-O) (5), whereas the addition of one equivalent of AgSbF 6 to 1 resulted in oxidation to THF-solvated octahedral [PcCr III (THF) 2 ]SbF 6 (6). The reduction of 1 with three sequential equivalents of KEt 3 BH resulted in the isolation of [K(DME) 4 ][Pc 3- Cr II ] (7), [K(DME) 4 ] 2 [Pc 4- Cr II ] (8) and [K 6 (DME) 4 ][Pc 4- Cr I ] 2 (9), respectively. The reduced products are deep purple in colour, with visible absorption maxima between 500-580 nm. The ring-reduced complexes 7 and 8 are monomeric, whereas 9 is a 1D chain of dinuclear [PcCr] 2 units with intercalated K + cations and supported by Cr-Cr interactions of 2.988(2) Å. Addition of four equivalents of KC 8 resulted in the demetallated product PcK 2 (DME) 4 (10), which has a 1D chain structure. The isolation and structural characterization of new PcCr complexes spanning five oxidation states, including rare examples of crystalline reduced Pc-ring species emphasizes the broad redox activity and stability of phthalocyanine-based complexes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photodynamic therapy of normal rat arteries after photosensitisation using disulphonated aluminium phthalocyanine and 5-aminolaevulinic acid.

PubMed Central

Grant, W. E.; Speight, P. M.; MacRobert, A. J.; Hopper, C.; Bown, S. G.

1994-01-01

Photodynamic therapy of cancer exposes adjacent arteries to the risk of injury and the possibility of haemorrhage and thrombosis. The nature of photodynamic injury to normal arteries has not been satisfactorily defined, and the ability of arteries to recover with time is unclear. To clarify these issues, we have investigated the effects of PDT on rat femoral arteries, using a second-generation photosensitiser, disulphonated aluminium phthalocyanine, and a new method of photosensitisation, using endogenous synthesis of protoporphyrin IX following systemic administration of 5-aminolaevulinic acid (ALA). Pharmacokinetic studies of sensitiser fluorescence were carried out to determine peak levels of sensitiser. Subsequently photodynamic therapy at times corresponding to maximal fluorescence was performed using two light doses, 100 and 250 J cm-2. The nature of injury sustained and recovery over a 6 month period was investigated. Three days following PDT, all vessels treated showed complete loss of endothelium, with death of all medial smooth muscle cells, leaving an acellular flaccid artery wall. No vascular occlusion, haemorrhage or thrombosis was found. A striking feature was the lack of inflammatory response in the vessel wall at any time studied. Re-endothelialisation occurred in all vessels by 2 weeks. The phthalocyanine group showed repopulation of the media with smooth muscle cells to be almost complete by 3 months. However, the ALA group failed to redevelop a muscular wall and remained dilated at 6 months. Luminal cross-sectional area of the ALA-treated group was significantly greater than both control and phthalocyanine groups at 6 months. All vessels remained patent. This study indicates that arteries exposed to PDT are not at risk of catastrophic haemorrhage or occlusion, a finding that is of significance for both the local treatment of tumours and the use of PDT as an intraoperative adjunct to surgery for the ablation of microscopic residual malignant disease. Images Figure 1 Figure 3 PMID:8018544

Synthesis of zinc phthalocyanine with large steric hindrance and its photovoltaic performance for dye-sensitized solar cells.

PubMed

Lin, Li; Peng, Bosi; Shi, Wenye; Guo, Yingying; Li, Renjie

2015-03-28

A zinc phthalocyanine (ZnPc) derivative (Zn-tri-PcNc-8) containing tri-benzonaphtho-condensed porphyrazine with one carboxylic and six diphenylphenoxy peripheral substitutions was designed and synthesized as a sensitizer for dye-sensitized solar cells (DSSCs). For the purpose of extending the absorption spectra while minimizing the formation of ZnPc molecular aggregates, bulky 2,6-diphenylphenoxy groups were used as electron donor moieties, and the carboxylic group as an anchoring group to graft the sensitizer onto the semiconductor. It was found that a TiO2-based solar cell sensitized by Zn-tri-PcNc-8 shows a maximum incident photon-to-current conversion efficiency in the red/near-IR light range (650-750 nm), and a solar cell sensitized at near room temperature (30 °C) for 48 h exhibits the best efficiency (3.01%). The efficiency was much higher than that (1.96%) for a solar cell sensitized by its analogue (Zn-tri-PcNc-2) having one carboxyl and three tert-butyl groups without chenodeoxycholic acid (CDCA), indicating that the introduction of six bulky diphenylphenoxy substitutions with large steric hindrance in the ZnPc macrocycle can effectively suppress the molecular aggregates, thus resulting in an improved conversion efficiency. The present results shed light on an effective solution to adjust the ZnPc property via chemical modification such as changing the "push-pull" effect and adding large steric hindrance substituents to further improve the efficiency of the phthalocyanine-sensitized solar cell.

Photodynamic effects of 31 different phthalocyanines on a human keratinocyte cell line.

PubMed

Jančula, Daniel; Maršálek, Blahoslav; Babica, Pavel

2013-10-01

Phthalocyanines (Pcs, colored macromolecular compounds with the ability to generate singlet oxygen) represent a promising group of photosensitizers due to their intense absorption in the red and UV portion of the spectrum which leads to their excitation. In order to characterize possible toxic effects associated with eventual practical use and application of these chemicals, we employed an in vitro cell culture model to evaluate cytotoxic effects of 31 different phthalocyanines using neutral red uptake assay. An immortalized human keratinocyte cell line HaCaT was exposed to the tested chemicals for 2 or 24h, either with or without illumination in the last 60 min of the exposure period. After 2- or 24-h exposure without illumination, no cytotoxic effects or weak cytotoxic effects were induced by any Pc under the study and EC50 values could not be obtained within the tested concentration ranges (1.25-20 mg L(-1) or 0.625-10 mg L(-1)). On the other hand, exposure to phthalocyanines under illumination induced a significant cytotoxic effect. The most pronounced cytotoxicity was elicited by Pcs previously shown to have high positive charge densities at peripheral parts of substituent groups, which is most likely the factor responsible for the binding of Pc to negatively charged membranes on the cell surface and thus guaranteeing the tight connection necessary for the singlet oxygen attack on the cell surface. Copyright © 2013 Elsevier Ltd. All rights reserved.

Electrocatalytic oxidation of Epinephrine and Norepinephrine at metal oxide doped phthalocyanine/MWCNT composite sensor

PubMed Central

Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Ebenso, Eno E.

2016-01-01

Glassy carbon electrode (GCE) was modified with metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, and the electrocatalytic properties were studied. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using FTIR, Raman and SEM techniques. The electrodes were characterized using cyclic voltammetry (CV) technique. The electrocatalytic behaviour of the electrode towards epinephrine (EP) and norepinephrine (NE) oxidation was investigated using CV and DPV. Result showed that GCE-MWCNT/Fe3O4/2,3-Nc, GCE-MWCNT/Fe3O429H,31H-Pc, GCE-MWCNT/ZnO/2,3-Nc and GCE-MWCNT/ZnO/29H,31H-Pc electrodes gave enhanced EP and NE current response. Stability study indicated that the four GCE-MWCNT/MO/Pc modified electrodes were stable against electrode fouling effect with the percentage NE current drop of 5.56–5.88% after 20 scans. GCE-MWCNT/Fe3O4/29H,31H-Pc gave the lowest limit of detection (4.6 μM) towards EP while MWCNT/ZnO/29H,31H-Pc gave the lowest limit of detection (1.7 μM) towards NE. The limit of detection and sensitivity of the electrodes compared well with literature. Electrocatalytic oxidation of EP and NE on GCE-MWCNT/MO/Pc electrodes was diffusion controlled with some adsorption of electro-oxidation reaction intermediates products. The electrodes were found to be electrochemically stable, reusable and can be used for the analysis of EP and NE in real life samples. PMID:27245690

Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

PubMed

Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

2012-11-05

In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

Synthesis and application of different phthalocyanine molecular sieve catalyst for oxidative desulfurization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Na; Li, Siwen; Wang, Jinyi

2015-05-15

M{sub 2}(PcAN){sub 2} (M=Fe, Co, Ni, Cu, Zn and Mn) anchored onto W-HZSM-5 (M{sub 2}(PcAN){sub 2}–W-HZSM-5) or the M{sub 2}(PcTN){sub 2} doping W-HZSM-5 (M{sub 2}(PcTN){sub 2}/W-HZSM-5) were prepared and their catalytic performances were tested for oxidative desulfurization in the presence of oxygen. Thiophene (T), benzothiophene (BT), and dibenzothiophene (DBT) were considered as sulfur compounds. Among zeolite-based catalysts, the Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 and Cu{sub 2}(PcTN){sub 2}/W-HZSM-5 showed superior desulfurization performance and the activity of selectivity followed the order: T>BT>DBT. The effects of phthalocyanine concentration were studied by UV–Vis and calcination temperature was obtained by TG-DSC for Cu{sub 2}(PcTN){sub 2}/W-HZSM-5. Catalysts weremore » characterized by EA, IR, XRD, SEM, TEM, ICP, and N{sub 2} adsorption. Reaction time, temperature and the amount of catalyst were investigated as the important parameters for optimization of the reaction. Furthermore, a possible process of oxidative desulfurization and the reaction products were proposed. - Graphical abstract: The ODS reaction schematic shows the reaction mechanism of ultra-deep desulfurization. The sulfur compounds are oxidized to their corresponding sulfoxides or sulfones through the use of oxygen and catalysts. The reaction process of ultra-deep desulfurization. - Highlights: • A kind of novel catalyst for deep desulfurization was synthesized. • Cu{sub 2}(PcAN){sub 2}–W-HZSM-5 exhibits excellent catalytic performance for desulfurization. • The reaction conditions that affect desulfurization efficiency are investigated. • The reaction process of model sulfur compounds is proposed.« less

Epitaxial growth and electronic properties of well ordered phthalocyanine heterojunctions MnPc/F{sub 16}CoPc

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindner, Susi; Mahns, Benjamin; Treske, Uwe

2014-09-07

We have prepared phthalocyanine heterojunctions out of MnPc and F{sub 16}CoPc, which were studied by means of X-ray absorption spectroscopy. This heterojunction is characterized by a charge transfer at the interface, resulting in charged MnPc{sup δ} {sup +} and F{sub 16}CoPc{sup δ} {sup −} species. Our data reveal that the molecules are well ordered and oriented parallel to the substrate surface. Furthermore, we demonstrate the filling of the Co 3d{sub z{sup 2}} orbital due to the charge transfer, which supports the explanation of the density functional theory, that the charge transfer is local and affects the metal centers only.

Phthalocyanine polymers

NASA Technical Reports Server (NTRS)

Achar, B. N.; Fohlen, G. M.; Parker, J. A. (Inventor)

1985-01-01

A method of forming 4,4',4'',4''' -tetraamino phthalocyanines involves reducing 4,4',4'',4''' -tetranitro phthalocyanines, polymerizing the metal tetraamino phthalocyanines with a tetracarboxylic dianhydride (preferably aromatic) or copolymerizing with a tetracarboxylic dianhydride and a diamine (preferably also aromatic) to produce amic acids which are then dehydrocyclized to imides. Thermally and oxidatively stable polymers result which form tough, flexible films, varnishes, adhesives, and fibers.

Controlling Growth Orientation of Phthalocyanine Films by Electrical Fields

NASA Technical Reports Server (NTRS)

Zhu, S.; Banks, C. E.; Frazier, D. O.; Ila, D.; Muntele, I.; Penn, B. G.; Sharma, A.; Rose, M. Franklin (Technical Monitor)

2001-01-01

Organic Phthalocyanine films have many applications ranging from data storage to various non-linear optical devices whose quality is affected by the growth orientation of Phthalocyanine films. Due to the structural and electrical properties of Phthalocyanine molecules, the film growth orientation depends strongly on the substrate surface states. In this presentation, an electrical field up to 4000 V/cm is introduced during film growth. The Phthalocyanine films are synthesized on quartz substrates using thermal evaporation. An intermediate layer is deposited on some substrates for introducing the electrical field. Scanning electron microscopy, x-ray diffraction, and Fourier transform infrared spectroscopy are used for measuring surface morphology, film structure, and optical properties, respectively. The comparison of Phthalocyanine films grown with and without the electrical field reveals different morphology, film density, and growth orientation, which eventually change optical properties of these films. These results suggest that the growth method in the electrical field can be used to synthesized Phthalocyanine films with a preferred crystal orientation as well as propose an interaction mechanism between the substrate surface and the depositing molecules. The details of growth conditions and of the growth model of how the Phthalocyanine molecules grow in the electrical field will be discussed.

Characterization of titanyl phthalocyanine (TiOPc) thin films by microscopic and spectroscopic method

NASA Astrophysics Data System (ADS)

Skonieczny, R.; Makowiecki, J.; Bursa, B.; Krzykowski, A.; Szybowicz, M.

2018-02-01

The titanyl phthalocyanine (TiOPc) thin film deposited on glass, silicon and gold substrate have been studied using Raman spectroscopy, atomic force microscopy (AFM), absorption and profilometry measurements. The TiOPc thin layers have been deposited at room temperature by the quasi-molecular beam evaporation technique. The Raman spectra have been recorded using micro Raman system equipped with a confocal microscope. Using surface Raman mapping techni que with polarized Raman spectra the polymorphic forms of the TiOPc thin films distribution have been obtained. The AFM height and phase image were examined in order to find surface features and morphology of the thin films. Additionally to compare experimental results, structure optimization and vibrational spectra calculation of single TiOPc molecule were performed using DFT calculations. The received results showed that the parameters like polymorphic form, grain size, roughness of the surface in TiOPc thin films can well characterize the obtained organic thin films structures in terms of their use in optoelectronics and photovoltaics devices.

Studies of anti-fibrillogenic activity of phthalocyanines of zirconium containing out-of-plane ligands.

PubMed

Kovalska, Vladyslava; Losytskyy, Mykhaylo; Chernii, Viktor; Volkova, Kateryna; Tretyakova, Iryna; Cherepanov, Vsevolod; Yarmoluk, Sergiy; Volkov, Sergiy

2012-01-01

Series of phthalocyanines of zirconium containing lysine, citric, nonanoic acid residues and dibenzolylmethane groups as out-of-plane ligands are firstly studied as inhibitors of fibrillogenesis using cyanine-based fluorescent inhibitory assay. It was shown that studied phthalocyanines at concentration of 20μM inhibited aggregation reaction on 38.5-57.6% and inhibitory activity of phthalocyanines depended on the chemical nature of out-of-plane ligand. For the most active compound PcZrLys(2) (zirconium phthalocyanine containing lysine fragment) the efficient inhibitor concentration was estimated to be 37μM. AFM studies have shown that in the presence of PcZrLys(2) the inhibition of fibrils formation and formation of spherical oligomeric aggregates took place. Due to the ability of phthalocyanines to decrease efficiently protein aggregation into the amyloid fibrils, modification of phthalocyanine molecules via out-of-plane substitutions was proposed as approach for design of anti-fibrillogenic agents with required properties. Copyright © 2011. Published by Elsevier Ltd.

Glycosylated Metal Phthalocyanines.

PubMed

Hanack, Michael

2015-11-10

In the first part; the syntheses of mono-; di-; and tetra-glycosylated phthalonitriles is described; which are the most used starting materials for the preparation of the corresponding glycosylated metal (mostly zinc) phthalocyanines. In the second section; the preparation of symmetric and unsymmetric mono-; tetra-; and octa- glycosylated zinc phthalocyanines are reviewed; in which the sugar is attached to the phthalocyanine macrocycle; either anomerically or via another one of its OH-groups.

Continuous wasteless ecologically safe technology of propylenecarbonate production in presence of phthalocyanine catalysts

DOEpatents

Afanasiev, Vladimir Vasilievich [Moscow, RU; Zefirov, Nikolai Serafimovich [Moscow, RU; Zalepugin, Dmitry Yurievich [Moscow, RU; Polyakov, Victor Stanislavovich [Moscow, RU; Tilkunova, Nataliya Alexandrovna [Moscow, RU; Tomilova, Larisa Godvigovna [Moscow, RU

2009-09-08

A continuous method of producing propylenecarbonate includes carboxylation of propylene oxide with carbon dioxide in presence of phthalocyanine catalyst on an inert carrier, using as the phthalocyanine catalyst at least one catalyst selected from the group consisting of not-substituted, methyl, ethyl, butyl, and tret butyl-substituted phthalocyanines of metals, including those containing counterions, and using as the carrier a hydrophobic carrier.

Assessing the potential roles of silicon and germanium phthalocyanines in planar heterojunction organic photovoltaic devices and how pentafluoro phenoxylation can enhance π-π interactions and device performance.

PubMed

Lessard, Benoît H; White, Robin T; Al-Amar, Mohammad; Plint, Trevor; Castrucci, Jeffrey S; Josey, David S; Lu, Zheng-Hong; Bender, Timothy P

2015-03-11

In this study, we have assessed the potential application of dichloro silicon phthalocyanine (Cl2-SiPc) and dichloro germanium phthalocyanine (Cl2-GePc) in modern planar heterojunction organic photovoltaic (PHJ OPV) devices. We have determined that Cl2-SiPc can act as an electron donating material when paired with C60 and that Cl2-SiPc or Cl2-GePc can also act as an electron acceptor material when paired with pentacene. These two materials enabled the harvesting of triplet energy resulting from the singlet fission process in pentacene. However, contributions to the generation of photocurrent were observed for Cl2-SiPc with no evidence of photocurrent contribution from Cl2-GePc. The result of our initial assessment established the potential for the application of SiPc and GePc in PHJ OPV devices. Thereafter, bis(pentafluoro phenoxy) silicon phthalocyanine (F10-SiPc) and bis(pentafluoro phenoxy) germanium phthalocyanine (F10-GePc) were synthesized and characterized. During thermal processing, it was discovered that F10-SiPc and F10-GePc underwent a reaction forming small amounts of difluoro SiPc (F2-SiPc) and difluoro GePc (F2-GePc). This undesirable reaction could be circumvented for F10-SiPc but not for F10-GePc. Using single crystal X-ray diffraction, it was determined that F10-SiPc has significantly enhanced π-π interactions compared with that of Cl2-SiPc, which had little to none. Unoptimized PHJ OPV devices based on F10-SiPc were fabricated and directly compared to those constructed from Cl2-SiPc, and in all cases, PHJ OPV devices based on F10-SiPc had significantly improved device characteristics compared to Cl2-SiPc.

Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

NASA Astrophysics Data System (ADS)

Zhang, Tiantian; Ma, Dongdong; Pan, Sujuan; Wu, Shijun; Jiang, Yufeng; Zeng, Di; Yang, Hongqin; Peng, Yiru

2016-10-01

Photo-induced electron transfer (PET) is an important and fundamental process in natural photosynthesis. To mimic such interesting PET process, a suitable donor and acceptor couple were properly chosen. Dendrimer phthalocyanines and their derivatives have emerged as promising materials for artificial photosynthesis systems. In this paper, the electron transfer between the light harvest dendrimer phthalocyanine (donor) and the 1,4-benzoquinone (acceptor) was studied by UV/Vis and fluorescence spectroscopic methods. It was found that fluorescence of phthalocyanine was quenched by benzoquinone (BQ) via excited state electron transfer, from the phthalocyanine to the BQ upon excitation at 610 nm. The Stern-Volmer constant (KSV) of electron transfer was calculated. Our study suggests that this dendritic phthalocyanine is an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.

Dielectric Properties of Reduced Graphene Oxide/Copper Phthalocyanine Nanocomposites Fabricated Through π- π Interaction

NASA Astrophysics Data System (ADS)

Wang, Zicheng; Wei, Renbo; Liu, Xiaobo

2017-01-01

Reduced graphene oxide/copper phthalocyanine nanocomposites are successfully prepared through a simple and effective two-step method, involving preferential reduction of graphene oxide and followed by self-assembly with copper phthalocyanine. The results of photographs, ultraviolet visible, x-ray diffraction, x-ray photoelectron spectroscopy, and scanning electron microscopy show that the in situ blending method can effectively facilitate graphene sheets to disperse homogenously in the copper phthalocyanine matrix through π- π interactions. As a result, the reduction of graphene oxide and restoration of the sp 2 carbon sites in graphene can enhance the dielectric properties and alternating current conductivity of copper phthalocyanine effectively.

CGP 55398, a liposomal Ge(IV) phthalocyanine bearing two axially ligated cholesterol moieties: a new potential agent for photodynamic therapy of tumours.

PubMed Central

Segalla, A.; Milanesi, C.; Jori, G.; Capraro, H. G.; Isele, U.; Schieweck, K.

1994-01-01

Ge(IV) phthalocyanine (GePc) with two axially ligated cholesterol moieties was prepared by chemical synthesis and incorporated in a monomeric state into small unilamellar liposomes (CGP 55398). Upon photoexcitation with light wavelengths around its intense absorption peak at 680 nm, GePc shows an efficient photosensitising activity towards biological substrates through a mechanism which largely involves the intermediacy of singlet oxygen. GePc injected systemically into mice bearing an intramuscularly implanted MS-2 fibrosarcoma is quantitatively transferred to serum lipoproteins and localises in the tumour tissue with good efficiency: at 24 h post injection the GePc content in the tumour is 0.74 and 1.87 micrograms per g of tissue with a tumour/peritumoral ratio of 4.35 and 5.67 for injected doses of 0.76 and 1.52 mg kg-1 respectively. At this time the red-light irradiation of the GePc-loaded fibrosarcoma causes a fast and massive tumour necrosis involving both malignant cells and blood vessels. Images Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 PMID:8180009

Electrorheological behavior of copper phthalocyanine-doped mesoporous TiO2 suspensions.

PubMed

Di, Kai; Zhu, Yihua; Yang, Xiaoling; Li, Chunzhong

2006-02-15

A type of anhydrous electrorheological (ER) material of copper phthalocyanine (CuPC)-doped mesoporous TiO2 was synthesized by in situ micelle-assisted incorporation CuPC during mesoporous TiO2 synthesis. TEM, XRD and the nitrogen adsorption-desorption isotherms demonstrated that the material had mesoporous structure and an anatase framework. The ER behavior of the suspensions of CuPC-doped mesoporous TiO2 in silicone oil with the different volume fractions was investigated under an applied electric field. It is found that the suspensions showed visible electrorheological behavior which were compared with that of pure TiO2. The dopants of CuPC molecules within the mesochannel of TiO2 mesoporous sieve improved the conductivity of the particles and produced a proper conductivity of approximately 10(-7) S m(-1). Dielectric spectra of the ER fluid were measured to examine the peak of epsilon'' should appear in the frequency range of 10(2)-10(5) Hz and have a large Deltaepsilon' in this frequency range. Therefore, the both properties may make a conjunct effect on electrorheological behavior.

The water soluble axially disubstituted silicon phthalocyanines: photophysicochemical properties and in vitro studies.

PubMed

Göksel, Meltem; Biyiklioglu, Zekeriya; Durmuş, Mahmut

2017-08-01

Two novel silicon(IV) phthalocyanines bearing 1,3-bis[3(dimethylamino)phenoxy]propan-2-ol or 1,3-bis[3(diethylamino)phenoxy]propan-2-ol groups at their axial positions were synthesized. These phthalocyanines were converted into their water soluble derivatives by the quaternization reaction with methyl iodide. The quaternized phthalocyanines show excellent solubility aqueous solutions without any aggregation which makes them potential photosensitizers for use in photodynamic therapy (PDT). For this reason, the photophysical and photochemical properties such as fluorescence quantum yields, lifetimes, singlet oxygen generation and photodegradation of both non-ionic (3 and 5) and quaternized cationic silicon(IV) phthalocyanines were investigated. Furthermore, the cytotoxicity of PDT was determined by colorimetric proliferation assay against to hepatocellular carcinoma (HuH-7) cancer cells. In this study, the cells were incubated with a novel water soluble silicon(IV) phthalocyanine derivatives and thereafter the cells were illuminated using broad-band incoherent light source.

Toward the Discovery of Effective Polycyclic Inhibitors of α-Synuclein Amyloid Assembly*

PubMed Central

Lamberto, Gonzalo R.; Torres-Monserrat, Valentina; Bertoncini, Carlos W.; Salvatella, Xavier; Zweckstetter, Markus; Griesinger, Christian; Fernández, Claudio O.

2011-01-01

The fibrillation of amyloidogenic proteins is a critical step in the etiology of neurodegenerative disorders such as Alzheimer and Parkinson diseases. There is major interest in the therapeutic intervention on such aberrant aggregation phenomena, and the utilization of polyaromatic scaffolds has lately received considerable attention. In this regard, the molecular and structural basis of the anti-amyloidogenicity of polyaromatic compounds, required to evolve this molecular scaffold toward therapeutic drugs, is not known in detail. We present here biophysical and biochemical studies that have enabled us to characterize the interaction of metal-substituted, tetrasulfonated phthalocyanines (PcTS) with α-synuclein (AS), the major protein component of amyloid-like deposits in Parkinson disease. The inhibitory activity of the assayed compounds on AS amyloid fibril formation decreases in the order PcTS[Ni(II)] ∼ PcTS > PcTS[Zn(II)] ≫ PcTS[Al(III)] ≈ 0. Using NMR and electronic absorption spectroscopies we demonstrated conclusively that the differences in binding capacity and anti-amyloid activity of phthalocyanines on AS are attributed to their relative ability to self-stack through π-π interactions, modulated by the nature of the metal ion bound at the molecule. Low order stacked aggregates of phthalocyanines were identified as the active amyloid inhibitory species, whose effects are mediated by residue specific interactions. Such sequence-specific anti-amyloid behavior of self-stacked phthalocyanines contrasts strongly with promiscuous amyloid inhibitors with self-association capabilities that act via nonspecific sequestration of AS molecules. The new findings reported here constitute an important contribution for future drug discovery efforts targeting amyloid formation. PMID:21795682

Growth and characterization of thin Cu-phthalocyanine films on MgO(001) layer for organic light-emitting diodes

PubMed Central

2012-01-01

Surface morphology and thermal stability of Cu-phthalocyanine (CuPc) films grown on an epitaxially grown MgO(001) layer were investigated by using atomic force microscope and X-ray diffractometer. The (002) textured β phase of CuPc films were prepared at room temperature beyond the epitaxial MgO/Fe/MgO(001) buffer layer by the vacuum deposition technique. The CuPc structure remained stable even after post-annealing at 350°C for 1 h under vacuum, which is an important advantage of device fabrication. In order to improve the device performance, we investigated also current-voltage-luminescence characteristics for the new top-emitting organic light-emitting diodes with different thicknesses of CuPc layer. PMID:23181826

Growth and characterization of thin Cu-phthalocyanine films on MgO(001) layer for organic light-emitting diodes.

PubMed

Bae, Yu Jeong; Lee, Nyun Jong; Kim, Tae Hee; Cho, Hyunduck; Lee, Changhee; Fleet, Luke; Hirohata, Atsufumi

2012-11-26

Surface morphology and thermal stability of Cu-phthalocyanine (CuPc) films grown on an epitaxially grown MgO(001) layer were investigated by using atomic force microscope and X-ray diffractometer. The (002) textured β phase of CuPc films were prepared at room temperature beyond the epitaxial MgO/Fe/MgO(001) buffer layer by the vacuum deposition technique. The CuPc structure remained stable even after post-annealing at 350°C for 1 h under vacuum, which is an important advantage of device fabrication. In order to improve the device performance, we investigated also current-voltage-luminescence characteristics for the new top-emitting organic light-emitting diodes with different thicknesses of CuPc layer.

New directions in phthalocyanine pigments

NASA Technical Reports Server (NTRS)

Trinh, Diep VO

1994-01-01

Phthalocyanines have been used as a pigment in coatings and related applications for many years. These pigments are some of the most stable organic pigments known. The phthalo blue and green pigments have been known to be ultraviolet (UV) stable and thermally stable to over 400 C. These phthalocyanines are both a semiconductor and photoconductor, exhibiting catalytic activity and photostabilization capability of polymers. Many metal free and metallic phthalocyanine derivatives have been prepared. Development of the new classes of phthalocyanine pigment could be used as coating on NASA spacecraft material such as glass to decrease the optical degradation from UV light, the outside of the space station modules for UV protection, and coating on solar cells to increase lifetime and efficiency.

Copper phthalocyanine films deposited by liquid-liquid interface recrystallization technique (LLIRCT).

PubMed

Patil, K R; Sathaye, S D; Hawaldar, R; Sathe, B R; Mandale, A B; Mitra, A

2007-11-15

The simple recrystallization process is innovatively used to obtain the nanoparticles of copper phthalocyanine by a simple method. Liquid-liquid interface recrystallization technique (LLIRCT) has been employed successfully to produce small sized copper phthalocyanine nanoparticles with diameter between 3-5 nm. The TEM-SAED studies revealed the formation of 3-5 nm sized with beta-phase dominated mixture of alpha and beta copper phthalocyanine nanoparticles. The XRD, SEM, and the UV-vis studies were further carried out to confirm the formation of copper phthalocyanine thin films. The cyclic voltametry (CV) studies conclude that redox reaction is totally reversible one electron transfer process. The process is attributed to Cu(II)/Cu(I) redox reaction.

Optical and electronic structure description of metal-doped phthalocyanines.

PubMed

Leal, Luciano Almeida; da Cunha, Wiliam Ferreira; Ribeiro Junior, Luiz Antonio; Pereira, Tamires Lima; Blawid, Stefan Michael; de Sousa Junior, Rafael Timóteo; da Silva Filho, Demétrio Antonio

2017-05-01

Phthalocyanines represent a crucial class of organic compounds with high technological appeal. By doping the center of these systems with metals, one obtains the so-called metal-phthalocyanines, whose property of being an effective electron donor allows for potentially interesting uses in organic electronics. In this sense, investigating optical and electronic structure changes in the phthalocyanine profiles in the presence of different metals is of fundamental importance for evaluating the appropriateness of the resulting system as far as these uses are concerned. In the present work, we carry out this kind of effort for phthalocyanines doped with different metals, namely, copper, nickel, and magnesium. Density functional theory was applied to obtain the absorption spectra, and electronic and structural properties of the complexes. Our results suggest that depending on the dopant, a different level of change is achieved. Moreover, electrostatic potential energy mapping shows how the charge distribution can be affected by solar radiation. Our contribution is crucial in describing the best possible candidates for use in different organic photovoltaic applications. Graphical Abstract Representation of meta-phthalocyanine systems. All calculations of this work are based on varying metal position along z axis, considering the z-axis has its zero point matching with the center of phthalocyanine cavityconsidering.

Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation.

PubMed

Yamada, Yasuyuki; Kato, Tatsuhisa; Tanaka, Kentaro

2016-08-22

A stacked assembly composed of a porphyrin and two phthalocyanines was prepared through fourfold rotaxane formation. Two phthalocyanine molecules, bearing four 24-crown-8 units, were assembled onto a porphyrin template incorporating four sidechains with two dialkylammonium ions each through pseudorotaxane formation between crown ether units and ammonium ions. The Staudinger phosphite reaction, as the stoppering reaction, resulted in the formation of the stacked heterotrimer composed of a porphyrin and two phthalocyanines connected through a fourfold rotaxane structure. UV/Vis spectroscopic and electrochemical studies of the heterotrimer indicated that there is a significant electronic interaction between the two phthalocyanine units due to the close stacking. The electrochemical oxidation process of the stacked heterotrimer was studied by cyclic voltammetry and spectroelectrochemistry. Electron paramagnetic resonance (EPR) spectroscopy of a dinuclear Cu(II) complex, in which two Cu(II) phthalocyanines were assembled on a metal-free porphyrin template, revealed that two Cu(II) phthalocyanines were located within the stacking distance, which resulted in an antiferromagnetic interaction between the two S=1/2 spins in the ground state of the Cu(2+) ions in the heterotrimer. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorination of phthalocyanine substituents: Improved photoproperties and enhanced photodynamic efficacy after optimal micellar formulations.

PubMed

Pucelik, Barbara; Gürol, Ilke; Ahsen, Vefa; Dumoulin, Fabienne; Dąbrowski, Janusz M

2016-11-29

A fluorinated phthalocyanine and its non-fluorinated analogue were selected to evaluate the potential enhancement of fluorination on photophysical, photochemical and redox properties as well as on biological activity in cellular and animal models. Due to the pharmacological relevance, the affinity of these phthalocyanines towards biological membranes (logP ow ) as well as their primary interaction with human serum albumin (HSA) or low-density lipoprotein (LDL) were determined. Water-dispersible drug formulation of phthalocyanines via Pluronic ® -based triblock copolymer micelles was prepared to avoid self-aggregation effects and to improve their delivery. The obtained results demonstrate that phthalocyanines incorporation into tunable-polymeric micelles significantly enhanced their cellular uptake and their photocytotoxicity. The improved biodistribution and photodynamic efficacy of the phthalocyanines-triblock copolymer conjugates was also confirmed in vivo in CT26 bearing BALB/c mice. PDT with both compounds led to tumor growth inhibition in all treated animals. Fluorinated phthalocyanine 2 turned out to be the most effective anticancer agent as the tumors of 20% of mice treated regressed completely and did not appear for over one year after treatment. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Changes in the adsorbate dipole layer with changing d-filling of the metal (II) (Co, Ni, Cu) phthalocyanines on Au(111).

PubMed

Xiao, Jie; Dowben, Peter A

2009-02-04

In combined photoemission and inverse photoemission spectroscopy studies, we observe changes in the metal phthalocyanine molecular orbital offsets with respect to the conducting gold substrate Fermi level, with the changing d-electron filling of the metal (II) (Co, Ni, Cu) phthalocyanines. The implication is that the interfacial dipole layer depends upon the choice of metal (Co, Ni, Cu) centers within the metal (II) phthalocyanines adsorbed on Au(111).

Electronic structure differences between H(2)-, Fe-, Co-, and Cu-phthalocyanine highly oriented thin films observed using NEXAFS spectroscopy.

PubMed

Willey, T M; Bagge-Hansen, M; Lee, J R I; Call, R; Landt, L; van Buuren, T; Colesniuc, C; Monton, C; Valmianski, I; Schuller, Ivan K

2013-07-21

Phthalocyanines, a class of macrocyclic, square planar molecules, are extensively studied as semiconductor materials for chemical sensors, dye-sensitized solar cells, and other applications. In this study, we use angular dependent near-edge x-ray absorption fine structure (NEXAFS) spectroscopy as a quantitative probe of the orientation and electronic structure of H2-, Fe-, Co-, and Cu-phthalocyanine molecular thin films. NEXAFS measurements at both the carbon and nitrogen K-edges reveal that phthalocyanine films deposited on sapphire have upright molecular orientations, while films up to 50 nm thick deposited on gold substrates contain prostrate molecules. Although great similarity is observed in the carbon and nitrogen K-edge NEXAFS spectra recorded for the films composed of prostrate molecules, the H2-phthalocyanine exhibits the cleanest angular dependence due to its purely out-of-plane π* resonances at the absorption onset. In contrast, organometallic-phthalocyanine nitrogen K-edges have a small in-plane resonance superimposed on this π* region that is due to a transition into molecular orbitals interacting with the 3dx(2)-y(2) empty state. NEXAFS spectra recorded at the metal L-edges for the prostrate films reveal dramatic variations in the angular dependence of specific resonances for the Cu-phthalocyanines compared with the Fe-, and Co-phthalocyanines. The Cu L3,2 edge exhibits a strong in-plane resonance, attributed to its b1g empty state with dx(2)-y(2) character at the Cu center. Conversely, the Fe- and Co- phthalocyanine L3,2 edges have strong out-of-plane resonances; these are attributed to transitions into not only b1g (dz(2)) but also eg states with dxz and dyz character at the metal center.

Kinetic of the Intracellular Incorporation of New Phthalocyanines Synthesized in mexico and Its Potential as Photosensibilizers in the Photodynamic Therapy

NASA Astrophysics Data System (ADS)

Aragón-Aguilar, Héctor; Ramón-Gallegos, Eva; Arenas-Huertero, Francisco Jesús; Contreras-Ramos, Alejandra; Cruz-Orea, Alfredo; Sosa-Sánchez, José Luís; Miranda, Maribel García

2008-08-01

The search of more specific and efficient photosensitizer in low oxygen tensions is a need in the Photodynamic Therapy (PDT). Phthalocyanines have demonstrated to have the above mentioned activity. The aim of this work was to determine the efficiency of PDT using two phthalocyanines synthesized in Mexico to eliminate melanoma cells. B16F0 melanoma mouse cells were exposed to concentrations from 8.95×10-5 to 0.733 m/mL of F16VoPc and F16NbPcC13 during 24h, afterwards cellular mortality was measured. One kinetic was realized to determine the intracellular incorporation of phthalocyanines by confocal microscopy at 1, 2, 4, 8, 16 and 24 h of exposition. The PDT was applied exposing the cells to innocuous concentration (that does not provoke cellular death with out irradiation) and irradiating with an argon laser at 100 J/cm2. For each phthalocyanine a control group was used; one group was not treated neither with light nor with phthalocyanine, the other group it was only irradiated. 24 h after treatment the citotoxicity was measured by Alamar blue assay. The innocuous concentration found for the phthalocyanines F16VoPc and F16NbPcC13 were 4.58×10-2 and 2.29×l0-2 mg/mL, respectively. The time of maximum intracellular accumulation for both phthalocyanines was 24 h. Only the F16VoPc had anticancerous activity and induced 31.7% of cellular death. The PDT might offer a potential alternative to the treatment of this cancer when is used the phthalocyanine F16VoPc.

Sensing response of copper phthalocyanine salt dispersed glass with organic vapours

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ridhi, R.; Sachdeva, Sheenam; Saini, G. S. S.

2016-05-06

Copper Phthalocyanine and other Metal Phthalocyanines are very flexible and tuned easily to modify their structural, spectroscopic, optical and electrical properties by either functionalizing them with various substituent groups or by replacing or adding a ligand to the central metal atom in the phthalocyanine ring and accordingly can be made sensitive and selective to various organic species or gaseous vapours. In the present work, we have dispersed Copper Phthalocyanine Salt (CuPcS) in sol-gel glass form using chemical route sol-gel method and studied its sensing mechanism with organic vapours like methanol and benzene and found that current increases onto their exposuremore » with vapours. A variation in the activation energies was also observed with exposure of vapours.« less

Sensing response of copper phthalocyanine salt dispersed glass with organic vapours

NASA Astrophysics Data System (ADS)

Ridhi, R.; Sachdeva, Sheenam; Saini, G. S. S.; Tripathi, S. K.

2016-05-01

Copper Phthalocyanine and other Metal Phthalocyanines are very flexible and tuned easily to modify their structural, spectroscopic, optical and electrical properties by either functionalizing them with various substituent groups or by replacing or adding a ligand to the central metal atom in the phthalocyanine ring and accordingly can be made sensitive and selective to various organic species or gaseous vapours. In the present work, we have dispersed Copper Phthalocyanine Salt (CuPcS) in sol-gel glass form using chemical route sol-gel method and studied its sensing mechanism with organic vapours like methanol and benzene and found that current increases onto their exposure with vapours. A variation in the activation energies was also observed with exposure of vapours.

Electronic structure, transport, and collective effects in molecular layered systems.

PubMed

Hahn, Torsten; Ludwig, Tim; Timm, Carsten; Kortus, Jens

2017-01-01

The great potential of organic heterostructures for organic device applications is exemplified by the targeted engineering of the electronic properties of phthalocyanine-based systems. The transport properties of two different phthalocyanine systems, a pure copper phthalocyanine (CoPc) and a flourinated copper phthalocyanine-manganese phthalocyanine (F 16 CoPc/MnPc) heterostructure, are investigated by means of density functional theory (DFT) and the non-equilibrium Green's function (NEGF) approach. Furthermore, a master-equation-based approach is used to include electronic correlations beyond the mean-field-type approximation of DFT. We describe the essential theoretical tools to obtain the parameters needed for the master equation from DFT results. Finally, an interacting molecular monolayer is considered within a master-equation approach.

Phthalocyanine Blends Improve Bulk Heterojunction Solar Cells

PubMed Central

Varotto, Alessandro; Nam, Chang-Yong; Radivojevic, Ivana; Tomé, Joao; Cavaleiro, José A.S.; Black, Charles T.; Drain, Charles Michael

2010-01-01

A core phthalocyanine platform allows engineering the solubility properties the band gap; shifting the maximum absorption toward the red. A simple method to increase the efficiency of heterojunction solar cells uses a self-organized blend of the phthalocyanine chromophores fabricated by solution processing. PMID:20136126

40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

Code of Federal Regulations, 2010 CFR

2010-07-01

..., metallized/Azo dye + metal acetate Direct dyes, Azo Disperse dyes, Azo and Vat Organic pigment Green 7/Copper phthalocyanine Organic pigments Organic pigments/Phthalocyanine pigments Organic pigments/Copper phthalocyanine (Blue Crude) Organic pigments, miscellaneous lakes and toners Lead Organic pigments, Quinacridines...

40 CFR Appendix B to Part 414 - Complexed Metal-Bearing Waste Streams

Code of Federal Regulations, 2011 CFR

2011-07-01

..., metallized/Azo dye + metal acetate Direct dyes, Azo Disperse dyes, Azo and Vat Organic pigment Green 7/Copper phthalocyanine Organic pigments Organic pigments/Phthalocyanine pigments Organic pigments/Copper phthalocyanine (Blue Crude) Organic pigments, miscellaneous lakes and toners Lead Organic pigments, Quinacridines...

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

PubMed

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

Saccharide substituted zinc phthalocyanines: optical properties, interaction with bovine serum albumin and near infrared fluorescence imaging for sentinel lymph nodes.

PubMed

Lu, Li; Lv, Feng; Cao, Bo; He, Xujun; Liu, Tianjun

2014-01-03

Saccharide-substituted zinc phthalocyanines, [2,9(10),16(17),23(24)-tetrakis((1-(β-D-glucose-2-yl)-1H-1,2,3-triazol-4-yl)methoxy)phthalocyaninato]zinc(II) and [2,9(10), 16(17),23(24)-tetrakis((1-(β-D-lactose-2-yl)-1H-1,2,3-triazol-4-yl)methoxy)phthalocyaninato] zinc(II), were evaluated as novel near infrared fluorescence agents. Their interaction with bovine serum albumin was investigated by fluorescence and circular dichroism spectroscopy and isothermal titration calorimetry. Near infrared imaging for sentinel lymph nodes in vivo was performed using nude mice as models. Results show that saccharide- substituted zinc phthalocyanines have favourable water solubility, good optical stability and high emission ability in the near infrared region. The interaction of lactose-substituted phthalocyanine with bovine serum albumin displays obvious differences to that of glucose- substituted phthalocyanine. Moreover, lactose-substituted phthalocyanine possesses obvious imaging effects for sentinel lymph nodes in vivo.

Preparation of Metalloporphyrin-Bound Superparamagnetic Silica Particles via "Click" Reaction.

PubMed

Hollingsworth, Javoris V; Bhupathiraju, N V S Dinesh K; Sun, Jirun; Lochner, Eric; Vicente, M Graça H; Russo, Paul S

2016-01-13

A facile approach using click chemistry is demonstrated for immobilization of metalloporphyrins onto the surface of silica-coated iron oxide particles. Oleic-acid stabilized iron oxide nanocrystals were prepared by thermal decomposition of iron(III) acetylacetonate. Their crystallinity, morphology, and superparamagnetism were determined using X-ray diffraction, transmission electron microscopy, and a superconducting quantum interference device. Monodisperse core-shell particles were produced in the silica-coating of iron oxide via microemulsion synthesis. Surface modification of these particles was performed in two steps, which included the reaction of silica-coated iron oxide particles with 3-bromopropyltrichlorosilane, followed by azido-functionalization with sodium azide. Monoalkylated porphyrins were prepared using the Williamson ether synthesis of commercially available tetra(4-hydroxyphenyl) porphyrin with propargyl bromide in the presence of a base. (1)H NMR and matrix-assisted laser desorption ionization confirmed the identity of the compounds. The prepared monoalkyne porphyrins were zinc-metalated prior to their introduction to azide-functionalized, silica-coated iron oxide particles in the click reaction. X-ray photoelectron spectroscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy were used to characterize the surface chemistry after each step in the reaction. In addition, particle size was determined using dynamic light scattering and microscopy. The presented methodology is versatile and can be extended to other photoreactive systems, such as phthalocyanines and boron-dipyrromethane, which may lead to new materials for optical, photonic, and biological applications.

Study on copper phthalocyanine and perylene-based ambipolar organic light-emitting field-effect transistors produced using neutral beam deposition method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Dae-Kyu; Oh, Jeong-Do; Shin, Eun-Sol

2014-04-28

The neutral cluster beam deposition (NCBD) method has been applied to the production and characterization of ambipolar, heterojunction-based organic light-emitting field-effect transistors (OLEFETs) with a top-contact, multi-digitated, long-channel geometry. Organic thin films of n-type N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide and p-type copper phthalocyanine were successively deposited on the hydroxyl-free polymethyl-methacrylate (PMMA)-coated SiO{sub 2} dielectrics using the NCBD method. Characterization of the morphological and structural properties of the organic active layers was performed using atomic force microscopy and X-ray diffraction. Various device parameters such as hole- and electron-carrier mobilities, threshold voltages, and electroluminescence (EL) were derived from the fits of the observed current-voltage andmore » current-voltage-light emission characteristics of OLEFETs. The OLEFETs demonstrated good field-effect characteristics, well-balanced ambipolarity, and substantial EL under ambient conditions. The device performance, which is strongly correlated with the surface morphology and the structural properties of the organic active layers, is discussed along with the operating conduction mechanism.« less

21 CFR 73.3124 - Phthalocyanine green.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Phthalocyanine green. 73.3124 Section 73.3124 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3124 Phthalocyanine green. (a) Identity...

21 CFR 73.3124 - Phthalocyanine green.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Phthalocyanine green. 73.3124 Section 73.3124 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3124 Phthalocyanine green. (a) Identity...

21 CFR 73.3124 - Phthalocyanine green.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Phthalocyanine green. 73.3124 Section 73.3124 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES GENERAL LISTING OF COLOR ADDITIVES EXEMPT FROM CERTIFICATION Medical Devices § 73.3124 Phthalocyanine green. (a) Identity...

High Performance Photodiode Based on p-Si/Copper Phthalocyanine Heterojunction.

PubMed

Zhong, Junkang; Peng, Yingquan; Zheng, Tingcai; Lv, Wenli; Ren, Qiang; Fobao, Huang; Ying, Wang; Chen, Zhen; Tang, Ying

2016-06-01

Hybrid organic-inorganic (HOI) photodiodes have both advantages of organic and inorganic materials, including compatibility of traditional Si-based semiconductor technology, low cost, high photosensitivity and high reliability, showing tremendous value in application. Red light sensitive HOI photodiodes based on the p-Si/copper phthalocyanine (CuPc) hetrojunction were fabricated and characterized. The effects of CuPc layer thickness on the performance were investigated, and an optimal layer thickness of around 30 nm was determined. An analytical expression is derived to describe the measured thickness dependence of the saturation photocurrent. For the device with optimal CuPc layer thickness, a photoresponsivity of 0.35 A/W and external quantum efficiency of 70% were obtained at 9 V reverse voltage bias and 655 nm light illumination of 0.451 mW. Furthermore, optical power dependent performances were investigated.

Phthalocyaninatoruthenium(II), Hexakis(dimethylsulfoxide)Phthalocyaninatoruthenium(II), and Hexadis(dimethylsulfoxide-d6)phthalocyanin-atoruthenium(II), Three Highly Selective NMR Shift Reagents.

DTIC Science & Technology

1977-07-18

dimethylsu lfoxi de-d6) phthalocyanin — atoruthenium (II), Three Highly Selective NMR Shift Reagents ( ~‘ iby j \\ / Clement K. Choy and F•lalcolm E. Kenney...Running head : Phthalocyaninatorut henium( II) Shift Reagents I NTRODUCT ION Previously, work on FePc (Pc = phthalocyanine li gand , C32H16N8) show- ing...RuPc and dimethylsulfoxide -d 6 were re cted together and the product isolated, An nmr spectrum of the product showed only phthalocyanine resorar.ces

Structure Optimization of 21,23-Core-Modified Porphyrins Absorbing Long-Wavelength Light as Potential Photosensitizers Against Breast Cancer Cells

DTIC Science & Technology

2007-04-01

the core nitrogen atom(s) of natural porphyrins with heavy atoms such as S, Se, and Te provides a red -shift in their absorption spectra [4- 7]. The...shown in red , b in green and c in blue Copyright © 2007 Society of Porphyrins & Phthalocyanines J. Porphyrins Phthalocyanines 2007; 11: 1-8 Y. YOU ET AL...shown in red , b in green and c in blue Copyright © 2007 Society of Porphyrins & Phthalocyanines J. Porphyrins Phthalocyanines 2007; 11: 1-8

Comparative Investigation of Peripheral and Nonperipheral Zinc Phthalocyanine-Based Polycarbazoles in Terms of Optical, Electrical, and Sensing Properties.

PubMed

Soganci, Tugba; Baygu, Yasemin; Kabay, Nilgün; Gök, Yaşar; Ak, Metin

2018-06-15

In this study, nonperipherally alkyl-linked carbazole conjugated novel zinc(II) phthalocyanine was synthesized by cyclotetramerization reaction of 6-(9 H-carbazol-9-yl)hexane-1-thiol and 3,6-bis(tosyloxy) phthalonitrile in a one-step reaction. Optical, electrical, and sensing properties of this super structured polycarbazole obtained by electropolymerization are compared with peripherally alkyl-linked polycarbazole-based zinc(II) phthalocyanine. It has been found that the attachment of alkyl-linked carbazoles to the phthalocyanine molecule in either peripheral or nonperipheral positions has a great effect on the optical and electrical properties and sensing ability of the resulting polycarbazole derivatives. P(n-ZnPc) has the highest electrochromic contrast (70.5%) among the derivatives of zinc(II) phthalocyanines in the literature. In addition to these, the sensor platform has been successfully established, and analytical optimizations have been carried out. When the sensors prepared with zinc(II) phthalocyanine are examined, it was specified that the n-ZnPc- co-TP/GOx was ranked first in the literature with high sensor response and stability. As a result, by changing of the peripheral and nonperipheral position of phthalocyanines, their physical properties can be tuned to meet the requirements of desired technological application.

Evaluation of antibacterial properties of novel phthalocyanines against Escherichia coli--comparison of analytical methods.

PubMed

Mikula, Premysl; Kalhotka, Libor; Jancula, Daniel; Zezulka, Stepan; Korinkova, Radka; Cerny, Jiri; Marsalek, Blahoslav; Toman, Petr

2014-09-05

We analyzed antibacterial effects of several novel phthalocyanines against Escherichia coli and evaluated the suitability of flow cytometry for the detection of antibacterial effects of phthalocyanines in comparison with routinely used cultivation. After 3h of exposure under cool white light eight cationic phthalocyanines showed very high antibacterial activity in the concentration of 2.00 mg L(-1) and four of them were even efficient in the concentration of 0.20 mg L(-1). Antibacterial activity of neutral and anionic compounds was considerably lower or even negligible. No antibacterial effect was detected when bacteria were exposed without illumination. Binding affinity to bacterial cells was found to represent an important parameter influencing phthalocyanine antibacterial activity that can be modified by total charge of peripheral substituents and by the presence of suitable functional groups inside them. Agglomeration of cells observed in suspensions treated with a higher concentration of certain cationic phthalocyanines (the strongest binders to bacterial membrane) affected cytometric measurements of total cell counts, thus without appropriate pretreatment of the sample before analysis this parameter seems not to be fully valid in the evaluation of phthalocyanine antibacterial activity. Cytometric measurement of cell membrane integrity appears to be a suitable and even more sensitive parameter than cultivation. Copyright © 2014 Elsevier B.V. All rights reserved.

Photodynamic therapy of melanoma using new, synthetic porphyrins and phthalocyanines as photosensitisers - a comparative study.

PubMed

Baldea, Ioana; Ion, Rodica-Mariana; Olteanu, Diana Elena; Nenu, Iuliana; Tudor, Diana; Filip, Adriana Gabriela

2015-01-01

Melanoma, a cancer that arises from melanocytes, is one of the most unresponsive cancers to known therapies and has a tendency to produce early metastases. Several studies showed encouraging results of the efficacy of photodynamic therapy (PDT) in melanoma, in different experimental settings in vitro and in vivo, as well as several clinical reports. Our study focuses on testing the antimelanoma efficacy of several new, synthetic photosensitisers (PS), from two different chemical classes, respectively four porphyrins and six phthalocyanines. These PS were tested in terms of cell toxicity and phototoxicity against a radial growth phase melanoma cell line (WM35), in vitro. Cells were exposed to different concentrations of the PS for 24h, washed, then irradiatied with red light (630 nm) 75 mJ/cm(2) for the porphyrins and 1 J/cm(2) for the phthalocyanines. Viability was measured using the MTS method. Two of the synthetic porphyrins, TTP and THNP, were active photosensitizers against WM35 melanoma in vitro. Phthalocyanines were effective in producing a dose dependent PDT-induced decrease in viability in a dose-dependent manner. The most efficient was Indium (III) Phthalocyanine chloride, a metal substituted phthalocyanine. The most efficient photosensitizers for PDT in melanoma cells were the phthalocyanines in terms of tumor cell photokilling and decreased dark toxicity.

Organic/carbon nanotubes hybrid thin films for chemical detection

NASA Astrophysics Data System (ADS)

Banimuslem, Hikmat Adnan

Metallophthalocyanines (MPcs) are classified as an important class of conjugated materials and they possess several advantages attributed to their unique chemical structure. Carbon nanotubes (CNT), on the other hand, are known to enhance the properties of nano-composites in the conjugated molecules, due to their one dimensional electronic skeleton, high surface area and high aspect ratio. In this thesis, work has been carried out on the investigation of different substituted metal-phthalocyanines with the aim of developing novel hybrid film structures which incorporates these phthalocyanines and single-walled carbon nanotubes (SWCNT) for chemical detection applications. Octa-substituted copper phthalocyanines (CuPcR[8]) have been characterised using UV-visible absorption spectroscopy. Obtained spectra have yielded an evidence of a thermally induced molecular reorganization in the films. Influence of the nature of substituents in the phthalocyanine molecule on the thin films conductivity was also investigated. Octa-substituted lead (II) phthalocyanines (PbPcR[8]) have also been characterized using UV-visible spectroscopy. Sandwich structures of ITO/PbPcR[8]/In were prepared to investigate the electronic conduction in PbPcR[8]. The variation in the J(V) behavior of the films as a result of heat treatment is expected to be caused by changes in the alignment inside the columnar stacking of the molecules of the films. Thin films of non-covalently hybridised SWCNT and tetra-substituted copper phthalocyanine (CuPcR[4]) molecules have been produced. FTIR, DC conductivity, SEM and AFM results have revealed the [mathematical equation]; interaction between SWCNTs and CuPCR[4] molecules and shown that films obtained from the acid-treated SWCNTs/CuPcR[4] hybrids demonstrated more homogenous surface. Thin films of pristine CuPCR[4] and CuPcR[4]/S WCNT were prepared by spin coating onto gold-coated glass slides and applied as active layers for the detection of benzo[a]pyrene, pentachlorophenol (PCP), 2-chlorophenol, diuron and simazine in water as well as amines vapours in ambient air utilizing total internal reflection spectroscopic ellipsometry (TIRE) as an optical detection method. Different concentrations of pesticides in water ranging from 1 to 25 mug/L have been examined. It was revealed that the shifts in [mathematical equation] spectra of CuPcR[4]SWCNT films were evidently larger than those produced by the pristine CuPcR[4] films, indicating largely improved films' sensitivity of the hybrid films. Adsorption of amines onto films' surfaces has been realised by monitoring changes in the phase shift [mathematical equation] of TIRE. Methylamine has shown higher sensitivity and lower response time among the studied amines. For all amines vapours, the sensitivity of SWCNT/CuPcR[4] hybrid films was higher than the sensitivity of pristine Cu[1]PCR[4] films. Further work has been carried out on hybrids of SWCNT with zinc phthalocyanines (ZnPc). Thin films of pristine SWCNT and SWCNT/ZnPc hybrids were prepared by drop casting onto interdigitated electrodes and applied as active layers to detect ammonia vapor by measuring electrical resistance changes. Influence of pyrene substituent in the phthalocyanine ring on the hybrid formation and their sensor response has also been verified.

Electrical and optical properties of C46H22N8O4KM (M=Co, Fe, Pb) molecular-material thin films prepared by the vacuum thermal evaporation technique.

PubMed

Sánchez-Vergara, M E; Ruiz Farfán, M A; Alvarez, J R; Ponce Pedraza, A; Ortiz, A; Alvarez Toledano, C

2007-03-01

In this work, the synthesis of new materials formed from metallic phthalocyanines (Pcs) and double potassium salt from 1,8-dihydroxianthraquinone is reported. The newly synthesized materials were characterized by scanning electron microscope (SEM), atomic force microscopy (AFM), infrared (IR) and Ultraviolet-visible (UV-vis) spectroscopy. The powder and thin-film samples of the synthesized materials, deposited by vacuum thermal evaporation, show the same intra-molecular bonds as in the IR spectroscopy studies, which suggests that the thermal evaporation process does not alter these bonds. The effect of temperature on conductivity and electrical conduction mechanism was measured in the thin films (approximately 137 nm thickness). They showed a semiconductor-like behaviour with an optical activation energy arising from indirect transitions of 2.15, 2.13 and 3.6eV for the C(46)H(22)N(8)O(4)KFe, C(46)H(22)N(8)O(4)KPb and C(46)H(22)N(8)O(4)KCo thin films.

Electronic properties of the interface between hexadecafluoro copper phthalocyanine and unsubstituted copper phthalocyanine films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Komolov, A. S., E-mail: akomolov07@ya.ru; Lazneva, E. F.; Pshenichnyuk, S. A.

2013-07-15

The formation of an interface during the deposition of unsubstituted copper phthalocyanine (CuPc) films on the surface of hexadecafluoro copper phthalocyanine (F{sub 16}-CuPc) films is studied. An incident low-energy electron beam with energies from 0 to 25 eV is used to test the surface under study according to the very-low-energy electron-diffraction technique (VLEED) in the mode of total current spectroscopy. For F{sub 16}-CuPc films, the structure of the maxima in the total current spectra and its main differences from the structure of the maxima for the CuPc film are determined in the energy range from 5 to 15 eV abovemore » the Fermi level. The differences in the structure of vacant electron orbitals for CuPc and F{sub 16}-CuPc are also revealed using density functional theory calculations. As a result of an analysis of variations in the intensities of the total current spectra of the CuPc and F{sub 16}-CuPc films, it is assumed that an intermediate layer up to 1 nm thick appears during the formation of an interface between these films, which is characterized by a spread of the features in the total current spectrum. The height, width, and change in the work function are determined for the studied F{sub 16}-CuPc/NuPc interface barrier. A decrease in the level of vacuum by 0.7 eV occurs in the boundary region, which corresponds to electron density transfer from the CuPc film toward the F{sub 16}-CuPc substrate.« less

Effect of diblock copolymer properties on the photophysical properties of dendrimer silicon phthalocyanine nanoconjugates

NASA Astrophysics Data System (ADS)

Chen, Kuizhi; Pan, Sujuan; Zhuang, Xuemei; Lv, Hafei; Que, Shoulin; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-07-01

1-2 generation poly(benzyl aryl ether) dendrimer silicon phthalocyanines with axially disubstituted cyano terminal functionalities (G n -DSiPc(CN)4 n , (G n = n-generation dendrimer, n = 1-2)) were synthesized. Their structures were characterized by elemental analysis, IR, 1H NMR, and ESI-MS. Polymeric nanoparticles (G n -DSiPc(CN)4 n /m) were formed through encapsulating G n -DSiPc(CN)4 n into three monomethoxyl poly(ethylene glycol)-poly(ɛ-caprolactone) diblock copolymers (MPEG-PCL) with different hydrophilic/hydrophobic proportion, respectively. The effect of dendritic generation and the hydrophilic/hydrophobic proportion of diblock copolymers on the UV/Vis and fluorescence spectra of G n -DSiPc(CN)4 n and G n -DSiPc(CN)4 n /m were studied. The photophysical properties of polymeric nanoparticles exhibited dendritic generation and hydrophilic/hydrophobic proportion dependence. The fluorescence intensities and lifetimes of G n -DSiPc(CN)4 n /m were lower than the corresponding free dendrimer phthalocyanines. G n -DSiPc(CN)4 n encapsulated into MPEG-PCL with hydrophilic/hydrophobic molecular weight ratio 2000:4000 exhibited excellent photophysical property. The mean diameter of MPEG2000-PCL2000 micelles was about 70 nm, which decreased when loaded with G n -DSiPc(CN)4 n .

Photocatalytic oxidation desulfurization of model diesel over phthalocyanine/La0.8Ce0.2NiO3.

PubMed

Li, Si-Wen; Li, Ying-Ying; Yang, Fei; Liu, Zhe; Gao, Rui-Min; Zhao, Jian-She

2015-12-15

A series highly efficient and stable metallophthalocyanine/La0.8Ce0.2NiO3 (ML/LCNO) photocatalysts were prepared by a facile sol-gel and immersion method. The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), TEM, N2 adsorption-desorption, and UV-Vis. The results revealed that LCNO calcined at 700°C possessed a perovskite structure with porous, and phthalocyanine not only adsorbed on the surface but also loaded in the pores of the LCNO oxide. The photocatalytic activities of the samples were evaluated by the photocatalytic oxidation of dibenzothiophene (DBT) under simulated sunlight irradiation. It was found that either macrocyclic structure or center metal of phthalocyanine had great influences on the photocatalytic activity of ML/LCNO. The oxidative reactivity of the different macrocycles was found in the order of MPc/LCNO>MTAP/LCNO>MPTpz/LCNO; which of different center metals was CoL/LCNO>FeL/LCNO>MnL/LCNO>NiL/LCNO>CuL/LCNO. The catalysts were reused several times with a slight decrease in activity. Furthermore, this kinetics of photocatalytic oxidation of DBT indicated that the reaction was a pseudo-first-order reaction. Copyright © 2015 Elsevier Inc. All rights reserved.

Immobilization of ruthenium phthalocyanine on silica-coated multi-wall partially oriented carbon nanotubes: Electrochemical detection of fenitrothion pesticide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Canevari, Thiago C., E-mail: tccanevari@gmail.com; Prado, Thiago M.; Cincotto, Fernando H.

Highlights: • Hybrid material, SiO{sub 2}/MWCNTs containing ruthenium phthalocyanine (RuPc) synthesized in situ. • Silica containing multi-walled carbon nanotube partially oriented. • Determination of pesticide fenitrothion in orange juice. - Abstract: This paper reports on the determination of the pesticide fenitrothion using a glassy carbon electrode modified with silica-coated, multi-walled, partially oriented carbon nanotubes, SiO{sub 2}/MWCNTs, containing ruthenium phthalocyanine (RuPc) synthesized in situ. The hybrid SiO{sub 2}/MWCNTs/RuPc material was characterized by UV–vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and differential pulse voltammetry. The modified electrode showed well-defined peaks in the presencemore » of fenitrothion in acetate buffer, pH 4.5, with a sensitivity of 0.0822 μA μM{sup −1} mm{sup −2} and a detection limit of 0.45 ppm. Notably, the modified SiO{sub 2}/MWCNTs/RuPc electrodes with did not suffer from significant influences in the presence of other organophosphorus pesticides during the determination of the fenitrothion pesticide. Moreover, this modified electrode showed excellent performance in the determination of fenitrothion in orange juice.« less

Structures and spectroscopic properties of nonperipherally and peripherally substituted metal-free phthalocyanines: a substitution effect study based on density functional theory calculations.

PubMed

Zhong, Aimin; Zhang, Yuexing; Bian, Yongzhong

2010-11-01

The molecular structures, molecular orbitals, atomic charges, electronic absorption spectra, and infrared (IR) and Raman spectra of a series of substituted metal-free phthalocyanine compounds with four (1, 3, 5, 7) or eight (2, 4, 6, 8) methoxyl (1, 2, 5, 6) or methylthio groups (3, 4, 7, 8) on the nonperipheral (1-4) or peripheral positions (5-8) of the phthalocyanine ring are studied by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. The calculated structural parameters and simulated electronic absorption and IR spectra are compared with the X-ray crystallography structures and the experimentally observed electronic absorption and IR spectra of the similar molecules, and good agreement between the calculated and experimental results is found. The substitution of the methoxyl or methylthio groups at the nonperipheral positions of the phthalocyanine ring has obvious effects on the molecular structure and spectroscopic properties of the metal-free phthalocyanine. Nonperipheral substitution has a more significant influence than peripheral substitution. The substitution effect increases with an increase in the number of substituents. The methylthio group shows more significant influence than the methoxyl group, despite the stronger electron-donating property of the methoxyl group than the methylthio group. The octa-methylthio-substituted metal-free phthalocyanine compounds have nonplanar structures whose low-lying occupied molecular orbitals and electronic absorption spectra are significantly changed by the substituents. The present systematical study will be helpful for understanding the relationship between structures and properties in phthalocyanine compounds and designing phthalocyanines with typical properties. Copyright © 2010 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aragon-Aguilar, Hector; Ramon-Gallegos, Eva; Arenas-Huertero, Francisco Jesus

The search of more specific and efficient photosensitizer in low oxygen tensions is a need in the Photodynamic Therapy (PDT). Phthalocyanines have demonstrated to have the above mentioned activity. The aim of this work was to determine the efficiency of PDT using two phthalocyanines synthesized in Mexico to eliminate melanoma cells. B16F0 melanoma mouse cells were exposed to concentrations from 8.95x10{sup -5} to 0.733 m/mL of F16VoPc and F16NbPcC13 during 24h, afterwards cellular mortality was measured. One kinetic was realized to determine the intracellular incorporation of phthalocyanines by confocal microscopy at 1, 2, 4, 8, 16 and 24 h ofmore » exposition. The PDT was applied exposing the cells to innocuous concentration (that does not provoke cellular death with out irradiation) and irradiating with an argon laser at 100 J/cm{sup 2}. For each phthalocyanine a control group was used; one group was not treated neither with light nor with phthalocyanine, the other group it was only irradiated. 24 h after treatment the citotoxicity was measured by Alamar blue assay. The innocuous concentration found for the phthalocyanines F16VoPc and F16NbPcC13 were 4.58x10-2 and 2.29xl0{sup -2} mg/mL, respectively. The time of maximum intracellular accumulation for both phthalocyanines was 24 h. Only the F16VoPc had anticancerous activity and induced 31.7% of cellular death. The PDT might offer a potential alternative to the treatment of this cancer when is used the phthalocyanine F16VoPc.« less

Binding Modes of Phthalocyanines to Amyloid β Peptide and Their Effects on Amyloid Fibril Formation.

PubMed

Valiente-Gabioud, Ariel A; Riedel, Dietmar; Outeiro, Tiago F; Menacho-Márquez, Mauricio A; Griesinger, Christian; Fernández, Claudio O

2018-03-13

The inherent tendency of proteins to convert from their native states into amyloid aggregates is associated with a range of human disorders, including Alzheimer's and Parkinson's diseases. In that sense, the use of small molecules as probes for the structural and toxic mechanism related to amyloid aggregation has become an active area of research. Compared with other compounds, the structural and molecular basis behind the inhibitory interaction of phthalocyanine tetrasulfonate (PcTS) with proteins such as αS and tau has been well established, contributing to a better understanding of the amyloid aggregation process in these proteins. We present here the structural characterization of the binding of PcTS and its Cu(II) and Zn(II)-loaded forms to the amyloid β-peptide (Aβ) and the impact of these interactions on the peptide amyloid fibril assembly. Elucidation of the PcTS binding modes to Aβ 40 revealed the involvement of specific aromatic and hydrophobic interactions in the formation of the Aβ 40 -PcTS complex, ascribed to a binding mode in which the planarity and hydrophobicity of the aromatic ring system in the phthalocyanine act as main structural determinants for the interaction. Our results demonstrated that formation of the Aβ 40 -PcTS complex does not interfere with the progression of the peptide toward the formation of amyloid fibrils. On the other hand, conjugation of Zn(II) but not Cu(II) at the center of the PcTS macrocyclic ring modified substantially the binding profile of this phthalocyanine to Aβ 40 and became crucial to reverse the effects of metal-free PcTS on the fibril assembly of the peptide. Overall, our results provide a firm basis to understand the structural rules directing phthalocyanine-protein interactions and their implications on the amyloid fibril assembly of the target proteins; in particular, our results contradict the hypothesis that PcTS might have similar mechanisms of action in slowing the formation of a variety of pathological aggregates. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Copper phthalocyanine-based CMPs with various internal structures and functionalities.

PubMed

Ding, Xuesong; Han, Bao-Hang

2015-08-18

Several kinds of copper phthalocyanine-based conjugated microporous polymers have been synthesized, which present enhanced long-wavelength photon absorption capability and high efficiency for singlet oxygen generation under low energy light irradiation. This strategy opens a facile avenue towards expanding the scope of phthalocyanine-based porous materials with various internal structures and functionalities.

Triblock copolymers encapsulated poly (aryl benzyl ether) dendrimer zinc(II) phthalocyanine nanoparticles for enhancement in vitro photodynamic efficacy.

PubMed

Huang, Yide; Yu, Huizhen; Lv, Huafei; Zhang, Hong; Ma, Dongdong; Yang, Hongqin; Xie, Shusen; Peng, Yiru

2016-12-01

A novel series of nanoparticles formed via an electrostatic interaction between the periphery of negatively charged 1-2 generation aryl benzyl ether dendrimer zinc (II) phthalocyanines and positively charged poly(L-lysin) segment of triblock copolymer, poly(L-lysin)-block-poly(ethylene glycol)-block-poly(L-lysin), was developed for the use as an effective photosensitizers in photodynamic therapy. The dynamic light scattering, atomic force microscopy showed that two nanoparticles has a relevant size of 80-150nm. The photophysical properties and singlet oxygen quantum yields of free dendrimer phthalocyanines and nanoparticles exhibited generation dependence. The intracellular uptake of dendrimer phthalocyanines in Hela cells was significantly elevated as they were incorporated into the micelles, but was inversely correlated with the generation of dendrimer phthalocyanines. The photocytotoxicity of dendrimer phthalocyanines incorporated into polymeric micelles was also increased. The presence of nanoparticles induced efficient cell death. Using a mitochondrial-sepcific dye rhodamine 123 (Rh123), our fluorescence microscopic result indicated that nanoparticles localized to the mitochondria. Copyright © 2016 Elsevier B.V. All rights reserved.

Photochemical studies and nanomolar photodynamic activities of phthalocyanines functionalized with 1,4,7-trioxanonyl moieties at their non-peripheral positions.

PubMed

Sobotta, Lukasz; Wierzchowski, Marcin; Mierzwicki, Michal; Gdaniec, Zofia; Mielcarek, Jadwiga; Persoons, Leentje; Goslinski, Tomasz; Balzarini, Jan

2016-02-01

Manganese(III), cobalt(II), copper(II), magnesium(II), zinc(II) and metal-free phthalocyanines, possessing 1,4,7-trioxanonyl substituents, at their non-peripheral positions, were subjected to photochemical, photodynamic and biological activity studies. Demetallated phthalocyanine and its metallated d-block analogues, with copper(II), cobalt(II), manganese(III) chloride, were found to be less efficient singlet oxygen generators in comparison to the zinc(II) analogue and zinc(II) phthalocyanine reference. Irradiation of several phthalocyanines for short time periods resulted in a substantially increased cytostatic activity against both suspension (leukemic/lymphoma at 85nM) and solid (cervix carcinoma at 72nM and melanoma at 81nM) tumour cell lines (up to 200-fold). Noteworthy is that enveloped viruses, such as for herpesvirus and influenza A virus, but not, non-enveloped virus strains, such as Coxsackie B4 virus and reovirus-1, exposed to irradiation in the presence of the phthalocyanines, markedly lost their infectivity potential. Copyright © 2015 Elsevier Inc. All rights reserved.

Syntheses of Octasubstituted Metal Phthalocyanines for Nonlinear Optics

NASA Technical Reports Server (NTRS)

Guo, Huaisong; Townsend, Cheryl; Sanghadasa, Mohan; Amai, Robert L. S.; Clark, Ronald D.; Penn, Benjamin

1998-01-01

Many organic materials can be used as nonlinear optical media. Phthalocyanines are of special interest because they show an unusually large third order nonlinear response, they are thermally and photochemically stable and they can be formed into oriented thin films (Langmuir-Blodgett films). They also can be easily complexed by a large variety of metals, which place them at the interface between organics and organometallics, and allows for fine tuning of the macro cycle electronic properties by the coordinated metal and substituent groups. A series of 1,4,8,11,15,18,22,25-octaalkoxy metal-free and metal phthalocyanines and 2,3,9,10,16,17,23,24-octaalkoxy metal phthalocyanines has been synthesized. Their nonlinear optical properties have been measured. The physical properties of all the phthalocyanines synthesized in this work are subject to both acid and solvent effects.

Ratiometric Fluorescent Detection of Pb2+ by FRET-Based Phthalocyanine-Porphyrin Dyads.

PubMed

Zhang, Dongli; Zhu, Mengliang; Zhao, Luyang; Zhang, Jinghui; Wang, Kang; Qi, Dongdong; Zhou, Yang; Bian, Yongzhong; Jiang, Jianzhuang

2017-12-04

Sensitive and selective detection of Pb 2+ is a very worthwhile endeavor in terms of both human health and environmental protection, as the heavy metal is fairly ubiquitous and highly toxic. In this study, we designed phthalocyanine-porphyrin (Pc-Por) heterodyads, namely, H 2 Pc-α-ZnPor (1) and H 2 Pc-β-ZnPor (2), by connecting a zinc(II) porphyrin moiety to the nonperipheral (α) or peripheral (β) position of a metal-free phthalocyanine moiety. Upon excitation at the porphyrin Soret region (420 nm), both of the dyads exhibited not only a porphyrin emission (605 nm) but also a phthalocyanine emission (ca. 700 nm), indicating the occurrence of intramolecular fluorescence resonance energy transfer (FRET) processes from the porphyrin donor to the phthalocyanine acceptor. The dyads can selectively bind Pb 2+ in the phthalocyanine core leading to a red shift of the phthalocyanine absorption and thus a decrease of spectral overlap between the porphyrin emission and phthalocyanine absorption, which in turn suppresses the intramolecular FRET. In addition, the binding of Pb 2+ can highly quench the emission of phthalocyanine by heavy-metal ion effects. The synergistic coupled functions endow the dyads with remarkable ratiometric fluorescent responses at two distinct wavelengths (F 605 /F 703 for 1 and F 605 /F 700 for 2). The emission intensity ratio increased as a linear function to the concentration of Pb 2+ in the range of 0-4.0 μM, whereas the detection limits were determined to be 3.4 × 10 -9 and 2.2 × 10 -8 M for 1 and 2, respectively. Furthermore, by comparative study of 1 and 2, the effects of distance and relative orientation between Pc and ZnPor fluorophores on the FRET efficiency and sensing performance were highlighted, which is helpful for further optimizing such FRET systems.

Circular dichroism spectroscopic investigation of double-decker phthalocyanine with G-Quadruplex as promising telomerase inhibitor

NASA Astrophysics Data System (ADS)

Baǧda, Efkan; Baǧda, Esra; Yabaş, Ebru

2017-01-01

In the present study, interaction of a double-decker phthalocyanine with two G-quadruplex DNA, Tel 21 and cMYC, was investigated. To the best of our knowledge, this is the first study about G-quadruplex-double decker phthalocyanine interaction. The spectrophotometric titration method was used for binding constant calculations. From the binding constants, it can be said that double-decker phthalocyanine more likely to bind Tel 21 rather than cMYC. The conformational changes upon binding were monitored via circular dichroism spectroscopy. The ethidium bromide replacement assay was investigated spectrofluorometrically.

Titanium and Ruthenium Phthalocyanines for NO2 Sensors: A Mini-Review

PubMed Central

Paoletti, Anna Maria; Pennesi, Giovanna; Rossi, Gentilina; Generosi, Amanda; Paci, Barbara; Albertini, Valerio Rossi

2009-01-01

This review presents studies devoted to the description and comprehension of phenomena connected with the sensing behaviour towards NO2 of films of two phthalocyanines, titanium bis-phthalocyanine and ruthenium phthalocyanine. Spectroscopic, conductometric, and morphological features recorded during exposure to the gas are explained and the mechanisms of gas-molecule interaction are also elucidated. The review also shows how X-ray reflectivity can be a useful tool for monitoring morphological parameters such as thickness and roughness that are demonstrated to be sensitive variables for monitoring the exposure of thin films of sensor materials to NO2 gas. PMID:22346697

The quest for biocompatible phthalocyanines for molecular imaging: Photophysics, relaxometry and cytotoxicity studies.

PubMed

Pinto, Sara M A; Tomé, Vanessa A; Calvete, Mário J F; Pereira, Mariette M; Burrows, Hugh D; Cardoso, Ana M S; Pallier, Agnès; C A Castro, M Margarida; Tóth, Éva; Geraldes, Carlos F G C

2016-01-01

Water soluble phthalocyanines bearing either four PEG500 or four choline substituents in the macrocyclic structure, as well as their Zn(II) and Mn(III) complexes were synthesized. The metal-free and Zn(II) complexes present relatively high fluorescence quantum yields (up to 0.30), while the Mn(III) complexes show no fluorescence as a consequence of rapid non-radiative deactivation of the Mn(III) phthalocyanine excited states through low-lying metal based or charge-transfer states. The effect of DMSO on the aggregation of the phthalocyanines was studied. It was not possible to obtain the Mn(II) complexes by reduction of the corresponding Mn(III) complexes due to the presence of electron donating substituents at the periphery of the phthalocyanines. The (1)H NMRD plots of the PEG500 and choline substituted Mn(III)-phthalocyanine complexes are typical of self-aggregated Mn(III) systems with r1 relaxivities of 4.0 and 5.7mM(-1)s(-1) at 20MHz and 25°C. The Mn(III)-phthalocyanine-PEG4 complex shows no significant cytotoxicity to HeLa cell cultures after 2h of incubation up to 2mM concentration. After 24h of cell exposure to the compound, significant toxicity was observed for all the concentrations tested with IC50 of 1.105mM. Copyright © 2015 Elsevier Inc. All rights reserved.

The effect of axial ligands on the quantum yield of singlet oxygen of new silicon phthalocyanine

NASA Astrophysics Data System (ADS)

Lv, Huafei; Zhang, Xuemei; Yu, Xinxin; Pan, Sujuan; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-10-01

The singlet oxygen (1O2) production abilitity is an important factor to assess their potential as effective of photosensitizers. In this paper, the 1O2 production rate, production rate constant and quantum yield of silicon(IV) phthalocyanine axially bearing 1-3 generation dendritic substituents were evaluated by a high performance liquid chromatographic method. The results show that the 1O2 production rate and production rate constant of these compounds increase gradually with dendritic generations increase. And the 1O2 quantum yield of silicon(IV) phthalocyanine with first generation dendritic ligand was the highest. This may be due to the isolation effect of the dendritic ligands on the phthalocyanine core. The parameters of the observed 1O2 production properties will provide valuable data for these dendrimer phthalocyanines as promising photosensitizer in PDT application.

Graphene and Carbon-Nanotube Nanohybrids Covalently Functionalized by Porphyrins and Phthalocyanines for Optoelectronic Properties.

PubMed

Wang, Aijian; Ye, Jun; Humphrey, Mark G; Zhang, Chi

2018-04-01

In recent years, there has been a rapid growth in studies of the optoelectronic properties of graphene, carbon nanotubes (CNTs), and their derivatives. The chemical functionalization of graphene and CNTs is a key requirement for the development of this field, but it remains a significant challenge. The focus here is on recent advances in constructing nanohybrids of graphene or CNTs covalently linked to porphyrins or phthalocyanines, as well as their application in nonlinear optics. Following a summary of the syntheses of nanohybrids constructed from graphene or CNTs and porphyrins or phthalocyanines, explicit intraconjugate electronic interactions between photoexcited porphyrins/phthalocyanines and graphene/CNTs are introduced classified by energy transfer, electron transfer, and charge transfer, and their optoelectronic applications are also highlighted. The major current challenges for the development of covalently linked nanohybrids of porphyrins or phthalocyanines and carbon nanostructures are also presented. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamics of copper-phthalocyanine molecules on Au/Ge(001).

PubMed

Sotthewes, K; Heimbuch, R; Zandvliet, H J W

2015-10-07

Spatially resolved current-time scanning tunneling spectroscopy combined with current-distance spectroscopy has been used to characterize the dynamic behavior of copper-phthalocyanine (CuPc) molecules adsorbed on a Au-modified Ge(001) surface. The analyzed CuPc molecules are adsorbed in a "molecular bridge" configuration, where two benzopyrrole groups (lobes) are connected to a Au-induced nanowire, whereas the other two lobes are connected to the adjacent nanowire. Three types of lobe configurations are found: a bright lobe, a dim lobe, and a fuzzy lobe. The dim and fuzzy lobes exhibit a well-defined switching behavior between two discrete levels, while the bright lobe shows a broad oscillation band. The observed dynamic behavior is induced by electrons that are injected into the LUMO+1 orbital of the CuPc molecule. By precisely adjusting the tip-molecule distance, the switching frequency of the lobes can be tuned accurately.

Dynamics of copper-phthalocyanine molecules on Au/Ge(001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sotthewes, K.; Heimbuch, R.; Zandvliet, H. J. W.

2015-10-07

Spatially resolved current-time scanning tunneling spectroscopy combined with current-distance spectroscopy has been used to characterize the dynamic behavior of copper-phthalocyanine (CuPc) molecules adsorbed on a Au-modified Ge(001) surface. The analyzed CuPc molecules are adsorbed in a “molecular bridge” configuration, where two benzopyrrole groups (lobes) are connected to a Au-induced nanowire, whereas the other two lobes are connected to the adjacent nanowire. Three types of lobe configurations are found: a bright lobe, a dim lobe, and a fuzzy lobe. The dim and fuzzy lobes exhibit a well-defined switching behavior between two discrete levels, while the bright lobe shows a broad oscillationmore » band. The observed dynamic behavior is induced by electrons that are injected into the LUMO+1 orbital of the CuPc molecule. By precisely adjusting the tip-molecule distance, the switching frequency of the lobes can be tuned accurately.« less

Preparation and surface functionalization of MWCNTs: study of the composite materials produced by the interaction with an iron phthalocyanine complex

PubMed Central

2011-01-01

Carbon nanotubes [CNTs] were synthesized by the catalytic vapor decomposition method. Thereafter, they were functionalized in order to incorporate the oxygen groups (OCNT) and subsequently the amine groups (ACNT). All three CNTs (the as-synthesized and functionalized) underwent reaction with an iron organometallic complex (FePcS), iron(III) phthalocyanine-4,4",4",4""-tetrasulfonic acid, in order to study the nature of the interaction between this complex and the CNTs and the potential formation of nanocomposite materials. Transmission electronic microscopy, N2 adsorption at 77 K, thermogravimetric analysis, temperature-programmed desorption, and X-ray photoelectron spectroscopy were the characterization techniques employed to confirm the successful functionalization of CNTs as well as the type of interaction existing with the FePcS. All results obtained led to the same conclusion: There were no specific chemical interactions between CNTs and the fixed FePcS. PMID:21711881

Preparation and surface functionalization of MWCNTs: study of the composite materials produced by the interaction with an iron phthalocyanine complex

NASA Astrophysics Data System (ADS)

Asedegbega-Nieto, Esther; Pérez-Cadenas, María; Carter, Jonathan; Anderson, James A.; Guerrero-Ruiz, Antonio

2011-04-01

Carbon nanotubes [CNTs] were synthesized by the catalytic vapor decomposition method. Thereafter, they were functionalized in order to incorporate the oxygen groups (OCNT) and subsequently the amine groups (ACNT). All three CNTs (the as-synthesized and functionalized) underwent reaction with an iron organometallic complex (FePcS), iron(III) phthalocyanine-4,4",4",4""-tetrasulfonic acid, in order to study the nature of the interaction between this complex and the CNTs and the potential formation of nanocomposite materials. Transmission electronic microscopy, N2 adsorption at 77 K, thermogravimetric analysis, temperature-programmed desorption, and X-ray photoelectron spectroscopy were the characterization techniques employed to confirm the successful functionalization of CNTs as well as the type of interaction existing with the FePcS. All results obtained led to the same conclusion: There were no specific chemical interactions between CNTs and the fixed FePcS.

Solvothermal preparation of phthalocyanine nanorod/rGO composites and their application to visible-light-responsive photocatalysts

NASA Astrophysics Data System (ADS)

Zhang, Shuai; Lu, Yongting; Zhang, Fan; Qu, Jie; Lin, Bencai; Yuan, Ningyi; Fang, Bijun; Ding, Jian-Ning

2016-09-01

Phthalocyanine (Pc) nanorod/reduced graphene oxide (rGO) composites were prepared by a simple solvothermal method, in which Pc nanosheet and graphene oxide (GO) suspensions were mixed in methanol. As characterized by scanning electron microscopy, transmission electron microscopy, and selected area electron diffraction, Pc nanorods with an amorphous structure and an average diameter of 250nm are partially covered by rGO sheets. In the photodegradation experiments, all the composites with different rGO content show enhanced photocatalytic activity for Rhodamine B decomposition under visible-light compared to pure Pc nanorods or rGO sheets. The enhanced photocatalytic activity shall be ascribed to the large surface area offered by rGO and the charge-transfer from Pc to rGO as indicated by the photoluminescence measurement, in which fluorescence intensity of the composites is much weaker than that of Pc nanorods.

Macromolecules for Inhibition of Corrosion and Wear

DTIC Science & Technology

1992-12-14

phthalocyanine TCAUPC tetrakis-(N-carboxy-12-aminoundecanoic acid ) phthalocyanine TCACPC tetrakis-(N-carboxy-6- aminocaproic acid ) phthalocyanine Table 2... acid ); (TCACPC] - tetrakis(N- carboxy-6- aminocaproic acid ). •* Containing p-hydroxy pyridine groups in the voids. 9 NAWCADWAR-92112-60 protection...fluids .......... ................................ 10 8 PFPE degradation in the presence of FeF 3 Lewis Acid ..... 11 9 The degradation mechanism for PFPE

Permanganate-assisted removal of PCR inhibitors during the DNA Chelex extraction from stained denim samples.

PubMed

Pîrlea, Sorina; Puiu, Mihaela; Răducan, Adina; Oancea, Dumitru

2017-03-01

In this study, it was demonstrated that the DNA Chelex extraction combined with the permanganate assisted-oxidation is highly efficient in removing the PCR inhibitors often found in clothing materials, such as phthalocyanine. The extraction assays were conducted in saliva, blood and epithelial cells samples mixed with three oxidation-resistant dye copper(II) α-phthalocyanine, copper(II) β-phthalocyanine and tetrasulfonated copper(II) β-phthalocyanine. After DNA amplification, all samples were able to provide full DNA profiles. The permanganate/Chelex system was tested further on denim-stained samples and displayed the same ability to remove the PCR inhibitors from the commercial textile materials.

Fluorescent Phthalocyanine Assembly Distinguishes Chiral Isomers of Different Types of Amino Acids and Sugars.

PubMed

Jiang, Yuying; Liu, Chenxi; Wang, Xiqian; Wang, Tianyu; Jiang, Jianzhuang

2017-07-25

The functions of some natural supramolecular architectures, such as ribosomes, are dependent on the recognition of different types of chiral biomolecules. However, the recognition of different types of chiral molecules (multiobject chiral recognition), such as amino acids and sugars, by independent and identically artificial supramolecular assembly, was rarely achieved. In this article, simple amphiphilic achiral phthalocyanine was found to form supramolecular chiral assemblies with charged water-soluble polymers upon host-guest interactions at the air/water interface. Among these systems, one identical phthalocyanine/poly(l-lysine) assembly not only can distinguish enantiomers of different amino acids but also can recognize several epimers of monose. The chiral recognitions were achieved by comparing either the steady-state fluorescence intensity or fluorescence quenching rate of phthalocyanine/poly(l-lysine) assemblies, before and after interaction with different small chiral molecules. It was demonstrated that the interactions between poly(l-lysine) and different small chiral molecules could change the aggregation of phthalocyanines. And the sensitivity of fluorescence and the excellent multiobject chiral recognition properties of the phthalocyanine/poly(l-lysine) assembly are dependent on the subtle molecular packing mode and the cooperation of different noncovalent interactions.

Elaboration of ammonia gas sensors based on electrodeposited polypyrrole--cobalt phthalocyanine hybrid films.

PubMed

Patois, Tilia; Sanchez, Jean-Baptiste; Berger, Franck; Fievet, Patrick; Segut, Olivier; Moutarlier, Virginie; Bouvet, Marcel; Lakard, Boris

2013-12-15

The electrochemical incorporation of a sulfonated cobalt phthalocyanine (sCoPc) in conducting polypyrrole (PPy) was done, in the presence or absence of LiClO4, in order to use the resulting hybrid material for the sensing of ammonia. After electrochemical deposition, the morphological features and structural properties of polypyrrole/phthalocyanine hybrid films were investigated and compared to those of polypyrrole films. A gas sensor consisting in platinum microelectrodes arrays was fabricated using silicon microtechnologies, and the polypyrrole and polypyrrole/phthalocyanine films were electrochemically deposited on the platinum microelectrodes arrays of this gas sensor. When exposed to ammonia, polymer-based gas sensors exhibited a decrease in conductance due to the electron exchange between ammonia and sensitive polymer-based layer. The characteristics of the gas sensors (response time, response amplitude, reversibility) were studied for ammonia concentrations varying from 1 ppm to 100 ppm. Polypyrrole/phthalocyanine films exhibited a high sensitivity and low detection limit to ammonia as well as a fast and reproducible response at room temperature. The response to ammonia exposition of polypyrrole films was found to be strongly enhanced thanks to the incorporation of the phthalocyanine in the polypyrrole matrix. © 2013 Elsevier B.V. All rights reserved.

Phthalocyanine-assisted photodynamic inactivation of pathogenic microorganisms

NASA Astrophysics Data System (ADS)

Mantareva, Vanya; Angelov, Ivan; Borissova, Ekaterina; Avramov, Latchezar; Kussovski, Vesselin

2007-03-01

The phthalocyanine zinc(II) and aluminum (III) complexes were studied to photoinactivate the bacterial strains, Staphylococcus aureus, methacillin-sensitive and methacillin-resistant, Pseudomonas aeruginosa and one yeast Candida albicans. The binding of phthalocyanines to bacteria and fungi cells was evaluated by the means of laserinduced fluorescence technique. The fluorescent spectra of dyes (650 - 800 nm) after direct excitation (635 nm) were measured as follows: 1. for the aqua supernatants obtained after 10 min cell incubation with the respected phthalocyanines (1.6 μmol.l -1), 2. for the washed from the unbound dye cells, and 3. for the organic extracts from the three times washed cells. Fluorescent intensities at the emission maximum (~690 nm) were compared to the spectra of the phthalocyanines in organic solutions. The phthalocyanines uptake data for bacteria and fungi were determined at different cell densities. Nevertheless the better fluorescence properties of AlPc (fluorescent quantum yield of 0.4 towards 0.3 for ZnPcs) the lower drug accumulation in microorganisms was obtained. PDI results indicated an intensive lowering of the bacterial survival of both strains of S. aureus treated with cationic ZnPcMe followed by the anionic ZnPcS, at irradiance of 100 mW cm -2 and fluence rate of 60 J cm -2. More resistant to phototreatment P. aeruginosa and morphologically complicated yeast C. albicans were successfully inactivated only with cationic ZnPcMe. These data indicate the promising future application of cationic phthalocyanine in photodynamic inactivation of pathogenic microorganisms.

Anti-fibrillogenic properties of phthalocyanines: effect of the out-of-plane ligands.

PubMed

Kovalska, V; Cherepanov, V; Losytskyy, M; Chernii, S; Senenko, A; Chernii, V; Tretyakova, I; Yarmoluk, S; Volkov, S

2014-12-15

The axially-coordinated phthalocyanines were previously reported as agents possessing strong anti-fibrillogenic properties. In the presented study we used the atomic force microscopy to investigate the intermediates and the products of insulin aggregation reaction formed in the presence of Zr and Hf phthalocyanine complexes that contain out-of-plane ligands of different size and nature. It is shown that while phthalocyanine-free insulin generated mostly amyloid fibrils with a diameter of 2-8nm and a length of up to 5μm, the presence of phthalocyanines with spatial bulky ligands (PcZrDbm2) leads to the redirection of the fibrillization reaction to the formation of the spherical oligomer aggregates with a diameter of 4-12nm. At the same time the phthalocyanine complex PcHfCl2 having the small-volume ligands induces the formation of large size insulin aggregates with a height of about 100nm that are supposed to be amorphous species. The study of the aggregation intermediates showed the certain similarity of the reaction passing for phthalocyanine-free insulin and insulin in the presence of PcZrDbm2. The large-size amorphous species were observed at the beginning of reaction, later they dissociated, leading to the formation and growth of the smaller size particles. The amyloid-sensitive cyanine dye 7519 demonstrates the strong fluorescent response both in the presence of fibrils and spherical oligomers, while it is non-sensitive to amorphous aggregates. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics.

PubMed

Bhupathiraju, N V S Dinesh K; Rizvi, Waqar; Batteas, James D; Drain, Charles Michael

2016-01-14

Porphyrinoids are robust heterocyclic dyes studied extensively for their applications in medicine and as photonic materials because of their tunable photophysical properties, diverse means of modifying the periphery, and the ability to chelate most transition metals. Commercial applications include their use as phthalocyanine dyes in optical discs, porphyrins in photodynamic therapy, and as oxygen sensors. Most applications of these dyes require exocyclic moieties to improve solubility, target diseases, modulate photophysical properties, or direct the self-organization into architectures with desired photonic properties. The synthesis of the porphyrinoid depends on the desired application, but the de novo synthesis often involves several steps, is time consuming, and results in low isolated yields. Thus, the application of core porphyrinoid platforms that can be rapidly and efficiently modified to evaluate new molecular architectures allows researchers to focus on the design concepts rather than the synthesis methods, and opens porphyrinoid chemistry to a broader scientific community. We have focused on several widely available, commercially viable porphyrinoids as platforms: meso-perfluorophenylporphyrin, perfluorophthalocyanine, and meso-perfluorophenylcorrole. The perfluorophenylporphyrin is readily converted to the chlorin, bacteriochlorin, and isobacteriochlorin. Derivatives of all six of these core platforms can be efficiently and controllably made via mild nucleophilic aromatic substitution reactions using primary S, N, and O nucleophiles bearing a wide variety of functional groups. The remaining fluoro groups enhance the photo and oxidative stability of the dyes and can serve as spectroscopic signatures to characterize the compounds or in imaging applications using (19)F NMR. This review provides an overview of the chemistry of fluorinated porphyrinoids that are being used as a platform to create libraries of photo-active compounds for applications in medicine and materials.

Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

2015-09-01

Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

Photodynamic inactivation of multiresistant bacteria (KPC) using zinc(II)phthalocyanines.

PubMed

Miretti, Mariana; Clementi, Romina; Tempesti, Tomas C; Baumgartner, María T

2017-09-15

The worldwide increase in antibiotic resistance has led to search of alternatives anti-microbial therapies such as photodynamic inactivation. The aim of this paper was to evaluate the photodynamic activity in vitro of a neutral and two cationic Zn phthalocyanines. Their photokilling activity was tested on Escherichia coli ATCC 25922 and Klebsiella pneumoniae Carbapenemase (KPC)-producing. After treating bacteria with phthalocyanines, the cultures were irradiated with white light. As a result, the bacteria were inactivated in presence of cationic phthalocyanines. The photoinactivation was dependent of the irradiation time and phthalocyanine concentration. The most effective photosensitizer on KPC-producing was Zinc(II)tetramethyltetrapyridino[2,3-b:2',3'-g:2″,3″-l:2‴,3‴-q]porphyrazinium methylsulfate (ZnTM2,3PyPz). After irradiation using the water soluble ZnTM2,3PyPz (3μM) the viability of KPC (30min of irradiation) and E. coli (10min of irradiation) decreased ≈99.995%. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interaction of cationic phthalocyanines with DNA. Importance of the structure of the substituents.

PubMed

López Zeballos, N C; Gauna, G A; García Vior, M C; Awruch, J; Dicelio, L E

2014-07-05

The interaction of novel zinc (II) cationic phthalocyanines with CT-DNA was studied using absorption and fluorescence spectroscopy, as well as thermal denaturation profiles. Results showed an electrostatic interaction between the phthalocyanines and CT-DNA. The properties of these phthalocyanines were compared taking the structure of the macrocycle peripheral substituents into account. 2,9(10),16(17),23(24)-tetrakis[(N-butyl-N-methylammonium)ethylsulfanyl]phthalocyaninatozinc(II) tetraiodide (Pc6) had a greater affinity for the CT-DNA helix than its bioisoster 2,9(10),16(17),23(24)-tetrakis[(N-dibutyl-N-methylammonium)ethoxy]phthalocyaninatozinc(II) tetraiodide (Pc7). 2,9(10),16(17),23(24)-tetrakis[(2-trimethylammonium)ethyl-sulfanyl]phthalocyaninatozinc(II) tetraiodide (Pc13) also carried a sulfur atom like Pc6, but linked to bulky substituents such as trimethylammonium groups. The planar aromatic region of the cationic phthalocyanines in this study appears to be unable to facilitate their intercalation with CT-DNA. Copyright © 2014 Elsevier B.V. All rights reserved.

Modelling copper-phthalocyanine/cobalt-phthalocyanine chains: towards magnetic quantum metamaterials.

PubMed

Wu, Wei

2014-07-23

The magnetic properties of a theoretically designed molecular chain structure CuCoPc2, in which copper-phthalocyanine (CuPc) and cobalt-phthalocyanine (CoPc) alternate, have been investigated across a range of chain structures. The computed exchange interaction for the α-phase CuCoPc2 is ∼ 5 K (ferromagnetic), in strong contrast to the anti-ferromagnetic interaction recently observed in CuPc and CoPc. The computed exchange interactions are strongly dependent on the stacking angle but weakly on the sliding angle, and peak at 20 K (ferromagnetic). These ferromagnetic interactions are expected to arise from direct exchange with the strong suppression of super-exchange interaction. These first-principles calculations show that π-conjugated molecules, such as phthalocyanine, could be used as building blocks for the design of magnetic materials. This therefore extends the concept of quantum metamaterials further into magnetism. The resulting new magnetic materials could find applications in the studies such as organic spintronics.

Electrochemical Interfaces and Electrode Processes.

DTIC Science & Technology

1984-08-15

reduction of 02 on such surfaces has been of special interest. Some of these complexes such as the iron tetrasulfonated phthalocyanines (TSPc) have high...high area carbon electrodes in porous carbon electrolyte structures (14,22,27). We have been successful in examining the Fe phthalocyanine and Co...Zagal, B. Z. Nikolic and R. R. Adzic, 1 May 1979. 50. A Mechanistic Study of 02 Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite

Virus inactivation under the photodynamic effect of phthalocyanine zinc(II) complexes.

PubMed

Remichkova, Mimi; Mukova, Luchia; Nikolaeva-Glomb, Lubomira; Nikolova, Nadya; Doumanova, Lubka; Mantareva, Vanya; Angelov, Ivan; Kussovski, Veselin; Galabov, Angel S

2017-03-01

Various metal phthalocyanines have been studied for their capacity for photodynamic effects on viruses. Two newly synthesized water-soluble phthalocyanine Zn(II) complexes with different charges, cationic methylpyridyloxy-substituted Zn(II)- phthalocyanine (ZnPcMe) and anionic sulfophenoxy-substituted Zn(II)-phthalocyanine (ZnPcS), were used for photoinactivation of two DNA-containing enveloped viruses (herpes simplex virus type 1 and vaccinia virus), two RNA-containing enveloped viruses (bovine viral diarrhea virus and Newcastle disease virus) and two nude viruses (the enterovirus Coxsackie B1, a RNA-containing virus, and human adenovirus 5, a DNA virus). These two differently charged phthalocyanine complexes showed an identical marked virucidal effect against herpes simplex virus type 1, which was one and the same at an irradiation lasting 5 or 20 min (Δlog=3.0 and 4.0, respectively). Towards vaccinia virus this effect was lower, Δlog=1.8 under the effect of ZnPcMe and 2.0 for ZnPcS. Bovine viral diarrhea virus manifested a moderate sensitivity to ZnPcMe (Δlog=1.8) and a pronounced one to ZnPcS at 5- and 20-min irradiation (Δlog=5.8 and 5.3, respectively). The complexes were unable to inactivate Newcastle disease virus, Coxsackievirus B1 and human adenovirus type 5.

Tunable charge transfer properties in metal-phthalocyanine heterojunctions.

PubMed

Siles, P F; Hahn, T; Salvan, G; Knupfer, M; Zhu, F; Zahn, D R T; Schmidt, O G

2016-04-28

Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.

Electrochemical Supercapacitor Electrodes from Sponge-like Graphene Nanoarchitectures with Ultrahigh Power Density.

PubMed

Xu, Zhanwei; Li, Zhi; Holt, Chris M B; Tan, Xuehai; Wang, Huanlei; Amirkhiz, Babak Shalchi; Stephenson, Tyler; Mitlin, David

2012-10-18

We employed a microwave synthesis process of cobalt phthalocyanine molecules templated by acid-functionalized multiwalled carbon nanotubes to create three-dimensional sponge-like graphene nanoarchitectures suited for ionic liquid-based electrochemical capacitor electrodes that operate at very high scan rates. The sequential "bottom-up" molecular synthesis and subsequent carbonization process took less than 20 min to complete. The 3D nanoarchitectures are able to deliver an energy density of 7.1 W·h kg(-1) even at an extra high power density of 48 000 W kg(-1). In addition, the ionic liquid supercapacitor based on this material works very well at room temperature due to its fully opened structures, which is ideal for the high-power energy application requiring more tolerance to temperature variation. Moreover, the structures are stable in both ionic liquids and 1 M H2SO4, retaining 90 and 98% capacitance after 10 000 cycles, respectively.

DFT study of the effect of substitution on the molecular structure of copper phthalocyanine

NASA Astrophysics Data System (ADS)

Kaur, Prabhjot; Sachdeva, Ritika; Singh, Sukhwinder; Saini, G. S. S.

2016-05-01

To study the effect of sulfonic acid group as substituent on the molecular structure of an organic compound copper Phthalocyanine, the optimized geometry, mulliken charges, energies and dipole momemts of copper phthalocyanine and copper phthalocyaninetetrasulfonic acid tetra sodium salt have been investigated using density functional theory. Also to predict the change in reactive sites after substitution, molecular electrostatic potential maps for both the molecules have been calculated.

DIAZOPHTHALOCYANINS AS REAGENTS FOR FINE STRUCTURAL CYTOCHEMISTRY

PubMed Central

Tice, Lois Withrow; Barrnett, Russell J.

1965-01-01

This paper reports the synthesis of 14 diazophthalocyanins containing Mg, Cu, or Pb as the chelated metal. To assess the usefulness of these compounds for fine structural cytochemistry, the relative coupling rates with naphthols were tested as well as the solubility of the resulting azo dyes. Three of the diazotates were reacted with tissue proteins in aldehyde-fixed material, and the density increases thus produced were compared in the electron microscope with those produced by staining similarly fixed material with the phthalocyanin dye, Alcian Blue. Finally, one of the diazotates was used as a capture reagent for the demonstration of the sites of acid phosphatase activity with the electron microscope. PMID:14283629

G-quadruplex and calf thymus DNA interaction of quaternized tetra and octa pyridyloxy substituted indium (III) phthalocyanines.

PubMed

Bağda, Efkan; Bağda, Esra; Durmuş, Mahmut

2017-10-01

The interactions of small molecules with G-quadruplex and double stranded DNA are important due to their potential biological and medical usages. In the present paper, the interactions of indium (III) phthalocyanines (quaternized 2,3,9,10,16,17,23,24-octakis-[(3-pyridyloxy) phthalocyaninato] chloroindium(III): OInPc and quaternized 2(3),9(10),16(17),23(24)-tetrakis-[(3-pyridyloxy) phthalocyaninato] chloroindium(III): TInPc) with hybrid G-quadruplex (Tel 21) and parallel G-quadruplexes (nucleolin, KRAS, c-MYC, vegf) were studied. The interactions of these phthalocyanines with ctDNA were also investigated. These interactions were measured by different spectroscopic techniques such as UV-Vis, fluorescence and circular dichroism. The UV-Vis spectroscopic data treated with Benesi-Hildebrand equation and Benesi-Hildebrand constants (K BH ) were calculated. These constants were found higher for octa peripheral pyridyloxy substituted phthalocyanine, OInPc. Besides, UV-Vis analysis showed that the interaction of G-quadruplexes with tetra peripheral pyridyloxy substituted phthalocyanine derivative (TInPc) resulted in removal of central indium (III) atom from the cavity of phthalocyanine macrocycle. The UV-Vis melting studies as well as fluorescence replacement techniques were also employed for clarification of mechanism. The binding mode of molecules with ct DNA was also supported with viscosity measurements. From the results, the stabilization and destabilization of G-quadruplex depending on the concentration of the OInPc and TInPc showed that these two indium (III) phthalocyanines have the potential of both the elucidation role of G-quadruplexes in gene expression and the usage in cancer therapy. Copyright © 2017. Published by Elsevier B.V.

Probing Supramolecular Interactions between a Crown Ether Appended Zinc Phthalocyanine and an Ammonium Group Appended to a C60 Derivative.

PubMed

Lederer, Marcus; Hahn, Uwe; Strub, Jean-Marc; Cianférani, Sarah; Van Dorsselaer, Alain; Nierengarten, Jean-François; Torres, Tomas; Guldi, Dirk M

2016-02-01

Self-assembly driven by crown ether complexation of zinc phthalocyanines equipped with one 18-crown-6 moiety and fullerenes bearing an ammonium head group afforded a novel donor-acceptor hybrid. In reference experiments, fullerenes containing a Boc-protected amine functionality have been probed. The circumvention of zinc phthalocyanine aggregation is important for the self-assembly, which required the addition of pyridine. From absorption and fluorescence titration assays, which provided sound and unambiguous evidence for mutual interactions between the electron donor and the electron acceptor within the hybrids, association constants in the order of 8.0×10 5  m -1 have been derived. The aforementioned is based on 1:1 stoichiometries, which have been independently confirmed by Job's plot measurements. In the excited state, which has been examined by transient absorption experiments, intermolecular charge separation evolves from the photoexcited zinc phthalocyanine to the fullerene subunit and leads to short-lived charge-separated states. Interestingly, photoexcitation of zinc phthalocyanine dimers/aggregates can also be followed by an intermolecular charge separation between vicinal phthalocyanines. These multicomponent supramolecular ensembles have also been shown by in-depth electrospray ionization mass spectrometry (ESI-MS) studies, giving rise to the formation and detection of a variety of non-covalently linked species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequential energy and charge transfer processes in mixed host-guest complexes of subphthalocyanine, porphyrin and phthalocyanine chromophores.

PubMed

Menting, Roel; Ng, Dennis K P; Röder, Beate; Ermilov, Eugeny A

2012-11-14

Porphyrins, phthalocyanines and subphthalocyanines are three attractive classes of chromophores with intriguing properties making them suitable for the design of artificial photosynthetic systems. The assembly of these components by a supramolecular approach is of particular interest as it provides a facile means to build multi-chromophoric arrays with various architectures and tuneable photophysical properties. In this paper, we show the formation of mixed host-guest supramolecular complexes that consist of a β-cyclodextrin-conjugated subphthalocyanine, a tetrasulfonated porphyrin and a series of silicon(IV) phthalocyanines substituted axially with two β-cyclodextrins via different spacers. We found that the three components form supramolecular complexes held by host-guest interactions in aqueous solution. Upon excitation of the subphthalocyanine part of the complex, the excitation energy is delivered to the phthalocyanine unit via excitation energy transfer and the porphyrin chromophore acts as an energy transfer bridge enabling this process. It was shown that photo-induced charge transfer also takes place. A sequential electron transfer process from the porphyrin unit to the phthalocyanine moiety and subsequently from the subphthalocyanine moiety to the porphyrin unit takes place, and the probability of this process is controlled by the linker between β-cyclodextrin and phthalocyanine. The lifetime of the charge-separated state was found to be 1.7 ns by transient absorption spectroscopy.

Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

NASA Astrophysics Data System (ADS)

Suzuki, Atsushi; Oku, Takeo

2016-02-01

Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of 13C, 14N and 1H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in 13C, 14N and 1H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

Iron phthalocyanine on Cu(111): Coverage-dependent assembly and symmetry breaking, temperature-induced homocoupling, and modification of the adsorbate-surface interaction by annealing.

PubMed

Snezhkova, Olesia; Bischoff, Felix; He, Yuanqin; Wiengarten, Alissa; Chaudhary, Shilpi; Johansson, Niclas; Schulte, Karina; Knudsen, Jan; Barth, Johannes V; Seufert, Knud; Auwärter, Willi; Schnadt, Joachim

2016-03-07

We have examined the geometric and electronic structures of iron phthalocyanine assemblies on a Cu(111) surface at different sub- to mono-layer coverages and the changes induced by thermal annealing at temperatures between 250 and 320 °C by scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy. The symmetry breaking observed in scanning tunneling microscopy images is found to be coverage dependent and to persist upon annealing. Further, we find that annealing to temperatures between 300 and 320 °C leads to both desorption of iron phthalocyanine molecules from the surface and their agglomeration. We see clear evidence of temperature-induced homocoupling reactions of the iron phthalocyanine molecules following dehydrogenation of their isoindole rings, similar to what has been observed for related tetrapyrroles on transition metal surfaces. Finally, spectroscopy indicates a modified substrate-adsorbate interaction upon annealing with a shortened bond distance. This finding could potentially explain a changed reactivity of Cu-supported iron phthalocyanine in comparison to that of the pristine compound.

Electronic Spectroscopy of Phthalocyanine and Porphyrin Derivatives in Superfluid Helium Nanodroplets.

PubMed

Slenczka, Alkwin

2017-07-25

Phthalocyanine and porphyrin were among the first organic compounds investigated by means of electronic spectroscopy in superfluid helium nanodroplets. Superfluid helium nanodroplets serve as a very gentle host system for preparing cold and isolated molecules. The uniqueness of helium nanodroplets is with respect to the superfluid phase which warrants the vanishing viscosity and, thus, minimal perturbation of the dopant species at a temperature as low as 0.37 K. These are ideal conditions for the study of molecular spectra in order to analyze structures as well as dynamic processes. Besides the investigation of the dopant species itself, molecular spectroscopy in helium droplets provides information on the helium droplet and in particular on microsolvation. This article, as part of a special issue on phthalocyanines and porphyrins, reviews electronic spectroscopy of phthalocyanine and porphyrin compounds in superfluid helium nanodroplets. In addition to the wide variety of medical as well as technical and synthetical aspects, this article discusses electronic spectroscopy of phthalocyanines and porphyrins in helium droplets in order to learn about both the dopant and the helium environment.

Quantitative surface-enhanced resonance Raman scattering of phthalocyanine-labelled oligonucleotides

PubMed Central

Macaskill, A.; Chernonosov, A. A.; Koval, V. V.; Lukyanets, E. A.; Fedorova, O. S.; Smith, W. E.; Faulds, K.; Graham, D.

2007-01-01

The evaluation of phthalocyanine labels for the surface-enhanced resonance Raman scattering (SERRS) detection of oligonucleotides is reported. Three phthalocyanine-labelled oligonucleotides were assessed, each containing a different metal centre. Detection limits for each labelled oligonucleotide were determined using two excitation frequencies where possible. Limits of detection as low as 2.8 × 10−11 mol. dm−3 were obtained which are comparable to standard fluorescently labelled probes used in previous SERRS studies. The identification of two phthalocyanine-labelled oligonucleotides without separation was also demonstrated indicating their suitability for multiplexing. This study extends the range of labels suitable for quantitative surface-enhanced resonance Raman scattering with silver nanoparticles and offers more flexibility and choice when considering SERRS for quantitative DNA detection. PMID:17289751

Photodynamic Effect of some Phthalocyanines on Enveloped and Naked Viruses.

PubMed

Nikolaeva-Glomb, L; Mukova, L; Nikolova, N; Kussovski, V; Doumanova, L; Mantareva, V; Angelov, I; Wöhrle, D; Galabov, A S

Activity of three photosensitizing phthalocyanine derivatives was tested for photodynamic inactivation towards two coated and two non-enveloped viruses - bovine viral diarrhea virus (BVDV), influenza virus A(H3N2), poliovirus type 1 (PV-1) and human adenovirus type 5 (HAdV5). In the case of coated viruses, a combination of virucidal and irradiation effects was registered by octa-methylpyridyloxy-substituted Ga phthalocyanine (Ga8) toward BVDV, whereas tetra-methylpyridyloxy-substituted Ga phthalocyanine (Ga4) revealed a marked photoinactivation only. No such effect was observed towards influenza A virus. In contrast, the photoinactivating potential of Ga4 and Ga8 marked very high values on naked viruses, especially on HAdV5, at which both the virucidal as well as the irradiation effects became combined.

High rectification in organic diodes based on liquid crystalline phthalocyanines.

PubMed

Apostol, Petru; Eccher, Juliana; Dotto, Marta Elisa Rosso; Costa, Cassiano Batesttin; Cazati, Thiago; Hillard, Elizabeth A; Bock, Harald; Bechtold, Ivan H

2015-12-28

The optical and electrical properties of mesogenic metal-free and metalated phthalocyanines (PCs) with a moderately sized and regioregular alkyl periphery were investigated. In solution, the individualized molecules show fluorescence lifetimes of 4-6 ns in THF. When deposited as solid thin films the materials exhibit significantly shorter fluorescence lifetimes with bi-exponential decay (1.4-1.8 ns; 0.2-0.4 ns) that testify to the formation of aggregates viaπ-π intermolecular interactions. In diode structures, their pronounced columnar order outbalances the unfavorable planar alignment and leads to excellent rectification behavior. Field-dependent charge carrier mobilities are obtained from the J-V curves in the trap-limited space-charge-limited current regime and demonstrate that the metalated PCs display an improved electrical response with respect to the metal-free homologue. The excited-state lifetime characterization suggest that the π-π intermolecular interactions are stronger for the metal-free PC, confirming that the metallic centre plays an important role in the charge transport inside these materials.

Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water

NASA Astrophysics Data System (ADS)

Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M.; Gnecco, Enrico

2014-06-01

The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

Molecular resolution friction microscopy of Cu phthalocyanine thin films on dolomite (104) in water.

PubMed

Nita, Paweł; Pimentel, Carlos; Luo, Feng; Milián-Medina, Begoña; Gierschner, Johannes; Pina, Carlos M; Gnecco, Enrico

2014-07-21

The reliability of ultrathin organic layers as active components for molecular electronic devices depends ultimately on an accurate characterization of the layer morphology and ability to withstand mechanical stresses on the nanoscale. To this end, since the molecular layers need to be electrically decoupled using thick insulating substrates, the use of AFM becomes mandatory. Here, we show how friction force microscopy (FFM) in water allows us to identify the orientation of copper(ii)phthalocyanine (CuPc) molecules previously self-assembled on a dolomite (104) mineral surface in ultra-high vacuum. The molecular features observed in the friction images show that the CuPc molecules are stacked in parallel rows with no preferential orientation with respect to the dolomite lattice, while the stacking features resemble well the single CuPc crystal structure. This proves that the substrate induction is low and makes friction force microscopy in water a suitable alternative to more demanding dynamic AFM techniques in ultra-high vacuum.

Tetracarboxy-phthalocyanines: From excited state dynamics to photodynamic inactivation against Bovine herpesvirus type 1.

PubMed

Cocca, Leandro H Z; Oliveira, Taise M A; Gotardo, Fernando; Teles, Amanda V; Menegatti, Ricardo; Siqueira, Jonathas P; Mendonça, Cleber R; Bataus, Luiz A M; Ribeiro, Anderson O; Souza, Thalita F M; Souza, Guilherme R L; Gonçalves, Pablo J; De Boni, Leonardo

2017-10-01

Herein we present the excited state dynamic of zinc and aluminum tetracarboxy-phthalocyanines (ZnPc and AlPc) and its application in the photodynamic inactivation (PDI) of Bovine herpesvirus type 1 (BoHV-1) in vitro. The excited state dynamic provides valuable data to describe the excited state properties of potential optical limiters and/or photosensitizers (PSs), such as: the excited state cross-sections, fluorescence lifetime and triplet state quantum yield. The excited state characterization was performed using three different Z-scan techniques: Single Pulse, White Light Continuum and Pulse Train. Considering the photodynamic inactivation of BoHV-1, an initial viral suspension containing 10 5.75 TCID 50 /mL was incubated with the PSs for 1h at 37°C under agitation and protected from light. The samples were placed in microtiter plates and irradiated (180mW/cm 2 ). During irradiation, a sample was taken every 15min and the viability of the virus was evaluated. The results show that both phthalocyanines were efficient against viruses. However, a higher photodynamic efficiency was observed by ZnPc, which can be attributed to its higher triplet and singlet quantum yields. The results presented here are important for animal health (treatment of BoHV-1) and also open up a field of studies to use AlPc and ZnPc as potential agents against a wide range of microorganisms of veterinary interest. Copyright © 2017 Elsevier B.V. All rights reserved.

Theoretical investigation of the electronic structure of a substituted nickel phthalocyanine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Prabhjot, E-mail: prabhphysics@gmail.com; Sachdeva, Ritika; Singh, Sukhwinder

2016-05-23

The optimized geometry and electronic structure of an organic compound nickel phthalocyanine tetrasulfonic acid tetra sodium salt have been investigated using density functional theory. We have also optimized the structure of nickel phthalocyanine tetrasulfonic acid tetra sodium salt in dimethyl sulfoxide to study effects of solvent on the electronic structure and transitions. Experimentally, the electronic transitions have been studied using UV-VIS spectroscopic technique. It is observed that the electronic transitions obtained from the theoretical studies generally agree with the experiment.

Molecular Association and Monolayer Formation of Soluble Phthalocyanine Compounds.

DTIC Science & Technology

1983-04-20

stable Langmuir - Blodgett monolayer to film pressures of 20 mN/m ant force-area curves indicate a dense packing of phthalocyanine units with molecular areas...8217which is monomeric and Cu, Ni, Pd and PtpdX4 wMyi,chjform larger complexes ranging from 2.7 to 4.1 molecular units. EachU.MCx*4 forms a stable Langmuir ... Blodgett monolayer to film pressures of 20 mN/in and force-area curves indicate a dense packing of phthalocyanine urits with molecul-ar areas

Aerospace Power Scholarly Research Program. Delivery Order 0011: Modeling Lithium-Ion Conducting Channel

DTIC Science & Technology

2005-12-01

Brinkmann, D. NMR, DSC, and conductivity study of a poly (ethylene oxide) complex electrolyte: PEO(LiClO4)x, Sol. St. Ionics 1986, 18-19, 295. (27...Electrochemical Characterizations of Dilithium Octacyanophthalocyanine Langmuir - Blodgett films, Langmuir 2002, 18, 2223. 20 ...phthalocyanine (Li2Pc) has been used in this development since it can undergo molecular self-assembly to form the ionic ally conducting channel. The

Porous silicon-copper phthalocyanine heterostructure based photoelectrochemical cell

NASA Astrophysics Data System (ADS)

A. Betty, C.; N, Padma; Arora, Shalav; Survaiya, Parth; Bhattacharya, Debarati; Choudhury, Sipra; Roy, Mainak

2018-01-01

A hybrid solar cell consisting of nanostructured p-type porous silicon (PS) deposited with visible light absorbing dye, Copper Phthalocyanine (CuPc) has been prepared in the photoelectrochemical cell configuration. P-type PS with (100) and (111) orientations which have different porous structures were used for studying the effects of the substrate morphology on the cell efficiency. Heterostructures were prepared by depositing three different thicknesses of CuPc for optimizing the cell efficiency. Structural and surface characterizations were studied using XRD, Raman, SEM and AFM on the PS-CuPc heterostructure. XRD spectrum on both plane silicon and porous silicon indicates the π-π stacking of CuPc with increased disorder for CuPc film on porous silicon. Electrochemical characterizations under sun light type radiation have been carried out to evaluate the photosensitivity of the heterostructure. Between the two different substrates, (100) PS gives better photocurrent, possibly due to the higher surface area and lower series resistance of the structure. Among the (100) PS substrates, (100) PS with 15 nm CuPc film gives Voc more than 1 V resulting in higher efficiency for the cell. The study suggests the scope for optimization of solar cell efficiency using various combinations of the substrate structure and thickness of the sensitizing layer.

Monoglycoconjugated phthalocyanines: effect of sugar and linkage on photodynamic activity.

PubMed

Lafont, Dominique; Zorlu, Yunus; Savoie, Huguette; Albrieux, Florian; Ahsen, Vefa; Boyle, Ross W; Dumoulin, Fabienne

2013-09-01

Click chemistry can be advantageously used to graft carbohydrates on phthalocyanines which are potent photosensitisers, but the effect of the presence of triazole moieties on photodynamic efficiency was not investigated systematically to date. The nature and linkage of the sugar were investigated in order to define structure-activity relationships. Two sets of monoglycoconjugated water-soluble phthalocyanines have been designed and their photodynamic activity and uptake investigated in HT-29 human colon adenocarcinoma cells. Carbohydrates: galactose, mannose or lactose were grafted onto Zn(II) phthalocyanines either by glycosylation or by click reaction. The triazole linkage formed by click conjugation lowered the biological efficiency for mannose and galactose, compared to classical glycosylation grafting. The mannose conjugate formed by glycosylation was the most photodynamically active, without correlation with the photosensitiser cell uptake. Copyright © 2012 Elsevier B.V. All rights reserved.

Antibacterial effect of cationic porphyrazines and anionic phthalocyanine and their interaction with plasmid DNA

NASA Astrophysics Data System (ADS)

Hassani, Leila; Hakimian, Fatemeh; Safaei, Elham; Fazeli, Zahra

2013-11-01

Resistance to antibiotics is a public health issue and identification of new antibacterial agents is one of the most important goals of pharmacological research. Among the novel developed antibacterial agents, porphyrin complexes and their derivatives are ideal candidates for use in medical applications. Phthalocyanines differ from porphyrins by having nitrogen atoms link the individual pyrrol units. The aza analogues of the phthalocyanines (azaPcs) such as tetramethylmetalloporphyrazines are heterocyclic Pc analogues. In this investigation, interaction of an anionic phthalocyanine (Cu(PcTs)) and two cationic tetrapyridinoporphyrazines including [Cu(2,3-tmtppa)]4+ and [Cu(3,4-tmtppa)]4+ complexes with plasmid DNA was studied using spectroscopic and gel electrophoresis methods. In addition, antibacterial effect of the complexes against Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria was investigated using dilution test method. The results indicated that both porphyrazines have significant antibacterial properties, but Cu(PcTs) has weak antibacterial effect. Compairing the binding of the phthalocyanine and the porphyrazines to DNA demonstrated that the interaction of cationic porphyrazines is stronger than the anionic phthalocyanine remarkably. The extent of hypochromicity and red shift of absorption spectra indicated preferential intercalation of the two porphyrazine into the base pairs of DNA helix. Gel electrophoresis result implied Cu(2,3-tmtppa) and Cu(3,4-tmtppa) are able to perform cleavage of the plasmid DNA. Consequently, DNA binding and cleavage might be one of the antibacterial mechanisms of the complexes.

Controlling the directionality of charge transfer in phthalocyaninato zinc sensitizer for a dye-sensitized solar cell: density functional theory studies.

PubMed

Wan, Liang; Qi, Dongdong; Zhang, Yuexing; Jiang, Jianzhuang

2011-01-28

Density functional theory (DFT) calculation on the molecular structures, charge distribution, molecular orbitals, electronic absorption spectra of a series of eight unsymmetrical phthalocyaninato zinc complexes with one peripheral (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent at 2 or 3 position as an electron-withdrawing group and a different number of electron-donating amino groups at the remaining peripheral positions (9, 10, 16, 17, 23, 24) of the phthalocyanine ring, namely ZnPc-β-A, ZnPc-β-A-I-NH(2), ZnPc-β-A-II-NH(2), ZnPc-β-A-III-NH(2), ZnPc-β-A-I,II-NH(2), ZnPc-β-A-I,III-NH(2), ZnPc-β-A-II,III-NH(2), and ZnPc-β-A-I,II,III-NH(2), reveals the effects of amino groups on the charge transfer properties of these phthalocyanine derivatives with a typical D-π-A electronic structure. The introduction of amino groups was revealed altering of the atomic charge distribution, lifting the frontier molecular orbital level, red-shift of the near-IR bands in the electronic absorption spectra, and finally resulting in enhanced charge transfer directionality for the phthalocyanine compounds. Along with the increase of the peripheral amino groups at the phthalocyanine ring from 0, 2, 4, to 6, the dihedral angle between the phthalocyanine ring and the average plane of the (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent increases from 0 to 3.3° in an irregular manner. This is in good contrast to the regular and significant change in the charge distribution, destabilization of frontier orbital energies, and red shift of near-IR bands of phthalocyanine compounds along the same order. In addition, comparative studies indicate the smaller effect of incorporating two amino groups onto the 16 and 17 than on 9 and 10 or 23 and 24 peripheral positions of the phthalocyanine ring onto the aforementioned electronic properties, suggesting the least effect on tuning the charge transfer property of the phthalocyanine compound via introducing two electron-donating amino groups onto the 16 and 17 peripheral positions. As expected, compound ZnPc-β-A-I,III-NH(2) with four amino groups at 9, 10, 23, and 24 positions of the phthalocyanine ring shows the best charge transfer directionality among the three phthalocyaninato zinc complexes with four peripheral amino groups.

Transport properties of two-dimensional metal-phthalocyanine junctions: An ab initio study

NASA Astrophysics Data System (ADS)

Liu, Shuang-Long; Wang, Yun-Peng; Li, Xiang-Guo; Cheng, Hai-Ping

We study two dimensional (2D) electronic/spintronic junctions made of metal-organic frameworks via first-principles simulation. The system consists of two Mn-phthalocyanine leads and a Ni-phthalocyanine center. A 2D Mn phthalocyanine sheet is ferromagnetic half metal and a 2D Ni phthalocyanine sheet is nonmagnetic semiconductor. Our results show that this system has a large tunnel magnetic resistance. The transmission coefficient at Fermi energy decays exponentially with the length of the central region which is not surprising. However, the transmission of the junction can be tuned using gate voltage by up to two orders of magnitude. The origin of the change lies in the mode matching between the lead and the center electronic states. Moreover, the threshold gate voltage varies with the length of the center region which provides a way of engineering the transport properties. Finally, we combine non-equilibrium Green's function and Boltzmann transport equation to compute conductance of the junction. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences (BES), under Contract No. DE-FG02-02ER45995. Computations were done using the utilities of NERSC and University of Florida Research Computing.

The Two Electron Oxidation of Cobalt Phthalocyanines by Thionyl Chloride: Implications for Lithium/Thionyl Chloride Batteries

DTIC Science & Technology

1989-10-20

Phthalocyanines by Thionyl Chloride. Implications for Lithium /Thionyl Chloride Batteries By P.A. Bernstein and A.B.P. Lever* D T IC in NOV.0 3.1W9. M...Thionyl Chloride. Implications forI Lithium /Thionvl Chloride Batteries 12 PERSONAL AUTHOR(S) P.A. Bernstein and A.B.P. Lever* 13a. TYPE OF REPORT 13b...SUBJECT TERMS (Continue on reverse if necessary and identify by olock numoer) FIELD GROUP SUB-GROUP .’ Phthalocyanine," Lithium Battery, Thionyl

trans-Bis(hexafluoroantimonato)(phthalocyaninato)copper(II).

PubMed

Gardberg, A S; Ibers, J A

2001-05-01

The title compound, trans-bis(hexafluoroantimonato-F)(phthalocyaninato-kappa(4)N(29,30,31,32))copper(II), [Cu(SbF(6))(2)(C(32)H(16)N(8))] or Cu(pc)(SbF(6))(2) (pc is phthalocyaninate), comprises a six-coordinate Cu atom, lying on an inversion center, bonded to four N atoms of a phthalocyanine ring and to F atoms of two trans SbF(6)(-) groups. The compound is presumed to consist of a Cu(II) center and a doubly oxidized phthalocyanine ring, by analogy with Cu(pc)(ReO(4))(2).

Femtosecond transient absorption, Raman, and electrochemistry studies of tetrasulfonated copper phthalocyanine in water solutions.

PubMed

Abramczyk, H; Brozek-Płuska, B; Kurczewski, K; Kurczewska, M; Szymczyk, I; Krzyczmonik, P; Błaszczyk, T; Scholl, H; Czajkowski, W

2006-07-20

Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfonated phthalocyanine Cu(tsPc)4-) in aqueous solution has been measured by femtosecond pump-probe transient absorption spectroscopy. The primary events initiated by the absorption of a photon occurring within the femtosecond time scale are discussed on the basis of the electron transfer mechanism between the adjacent phthalocyanine rings proposed recently in our laboratory. The femtosecond transient absorption results are compared with the low temperature emission spectra obtained with Raman spectroscopy and the voltammetric curves.

Improved Photodynamic Efficacy of Zn(II) Phthalocyanines via Glycerol Substitution

PubMed Central

Chin, Yunni; Lim, Siang Hui; Zorlu, Yunus; Ahsen, Vefa; Kiew, Lik Voon; Chung, Lip Yong; Dumoulin, Fabienne; Lee, Hong Boon

2014-01-01

Phthalocyanines are excellent photosensitizers for photodynamic therapy as they have strong absorbance in the near infra-red region which is most relevant for in vivo activation in deeper tissular regions. However, most phthalocyanines present two major challenges, ie, a strong tendency to aggregate and low water-solubility, limiting their effective usage clinically. In the present study, we evaluated the potential enhancement capability of glycerol substitution on the photodynamic properties of zinc (II) phthalocyanines (ZnPc). Three glycerol substituted ZnPc, 1–3, (tetra peripherally, tetra non-peripherally and mono iodinated tri non-peripherally respectively) were evaluated in terms of their spectroscopic properties, rate of singlet oxygen generation, partition coefficient (log P), intracellular uptake, photo-induced cytotoxicity and vascular occlusion efficiency. Tetrasulfonated ZnPc (ZnPcS4) was included as a reference compound. Here, we showed that 1–3 exhibited 10–100 nm red-shifted absorption peaks with higher molar absorptivity, and at least two-fold greater singlet oxygen generation rates compared to ZnPcS4. Meanwhile, phthalocyanines 1 and 2 showed more hydrophilic log P values than 3 consistent with the number of glycerol attachments but 3 was most readily taken up by cells compared to the rest. Both phthalocyanines 2 and 3 exhibited potent phototoxicity against MCF-7, HCT-116 and HSC-2 cancer cell-lines with IC50 ranging 2.8–3.2 µM and 0.04–0.06 µM respectively, while 1 and ZnPcS4 (up to 100 µM) failed to yield determinable IC50 values. In terms of vascular occlusion efficiency, phthalocyanine 3 showed better effects than 2 by causing total occlusion of vessels with diameter <70 µm of the chorioallantoic membrane. Meanwhile, no detectable vascular occlusion was observed for ZnPcS4 with treatment under similar experimental conditions. These findings provide evidence that glycerol substitution, in particular in structures 2 and 3, is able to improve the photodynamic properties of ZnPc. PMID:24840576

Improved photodynamic efficacy of Zn(II) phthalocyanines via glycerol substitution.

PubMed

Chin, Yunni; Lim, Siang Hui; Zorlu, Yunus; Ahsen, Vefa; Kiew, Lik Voon; Chung, Lip Yong; Dumoulin, Fabienne; Lee, Hong Boon

2014-01-01

Phthalocyanines are excellent photosensitizers for photodynamic therapy as they have strong absorbance in the near infra-red region which is most relevant for in vivo activation in deeper tissular regions. However, most phthalocyanines present two major challenges, ie, a strong tendency to aggregate and low water-solubility, limiting their effective usage clinically. In the present study, we evaluated the potential enhancement capability of glycerol substitution on the photodynamic properties of zinc (II) phthalocyanines (ZnPc). Three glycerol substituted ZnPc, 1-3, (tetra peripherally, tetra non-peripherally and mono iodinated tri non-peripherally respectively) were evaluated in terms of their spectroscopic properties, rate of singlet oxygen generation, partition coefficient (log P), intracellular uptake, photo-induced cytotoxicity and vascular occlusion efficiency. Tetrasulfonated ZnPc (ZnPcS4) was included as a reference compound. Here, we showed that 1-3 exhibited 10-100 nm red-shifted absorption peaks with higher molar absorptivity, and at least two-fold greater singlet oxygen generation rates compared to ZnPcS4. Meanwhile, phthalocyanines 1 and 2 showed more hydrophilic log P values than 3 consistent with the number of glycerol attachments but 3 was most readily taken up by cells compared to the rest. Both phthalocyanines 2 and 3 exhibited potent phototoxicity against MCF-7, HCT-116 and HSC-2 cancer cell-lines with IC50 ranging 2.8-3.2 µM and 0.04-0.06 µM respectively, while 1 and ZnPcS4 (up to 100 µM) failed to yield determinable IC50 values. In terms of vascular occlusion efficiency, phthalocyanine 3 showed better effects than 2 by causing total occlusion of vessels with diameter <70 µm of the chorioallantoic membrane. Meanwhile, no detectable vascular occlusion was observed for ZnPcS4 with treatment under similar experimental conditions. These findings provide evidence that glycerol substitution, in particular in structures 2 and 3, is able to improve the photodynamic properties of ZnPc.

Hybrid ZnO/phthalocyanine photovoltaic device with highly resistive ZnO intermediate layer.

PubMed

Izaki, Masanobu; Chizaki, Ryo; Saito, Takamasa; Murata, Kazufumi; Sasano, Junji; Shinagawa, Tsutomu

2013-10-09

We report a hybrid photovoltaic device composed of a 3.3 eV bandgap zinc oxide (ZnO) semiconductor and metal-free phthalocyanine layers and the effects of the insertion of the highly resistive ZnO buffer layer on the electrical characteristics of the rectification feature and photovoltaic performance. The hybrid photovoltaic devices have been constructed by electrodeposition of the 300 nm thick ZnO layer in a simple zinc nitrate aqueous solution followed by vacuum evaporation of 50-400 nm thick-phthalocyanine layers. The ZnO layers with the resistivity of 1.8 × 10(3) and 1 × 10(8) Ω cm were prepared by adjusting the cathodic current density and were installed into the hybrid photovoltaic devices as the n-type and buffer layer, respectively. The phthalocyanine layers with the characteristic monoclinic lattice showed a characteristic optical absorption feature regardless of the thickness, but the preferred orientation changed depending on the thickness. The ZnO buffer-free hybrid 50 nm thick phthalocyanine/n-ZnO photovoltaic device showed a rectification feature but possessed a poor photovoltaic performance with a conversion efficiency of 7.5 × 10(-7) %, open circuit voltage of 0.041 V, and short circuit current density of 8.0 × 10(-5) mA cm(-2). The insertion of the ZnO buffer layer between the n-ZnO and phthalocyanine layers induced improvements in both the rectification feature and photovoltaic performance. The excellent rectification feature with a rectification ratio of 3188 and ideally factor of 1.29 was obtained for the hybrid 200 nm thick phthalocyanine/ZnO buffer/n-ZnO photovoltaic device, and the hybrid photovoltaic device possessed an improved photovoltaic performance with the conversion efficiency of 0.0016%, open circuit voltage of 0.31 V, and short circuit current density of 0.015 mA cm(-2).

Selective detection of vapor phase hydrogen peroxide with phthalocyanine chemiresistors.

PubMed

Bohrer, Forest I; Colesniuc, Corneliu N; Park, Jeongwon; Schuller, Ivan K; Kummel, Andrew C; Trogler, William C

2008-03-26

The use of hydrogen peroxide as a precursor to improvised explosives has made its detection a topic of critical importance. Chemiresistor arrays comprised of 50 nm thick films of metallophthalocyanines (MPcs) are redox selective vapor sensors of hydrogen peroxide. Hydrogen peroxide is shown to decrease currents in cobalt phthalocyanine sensors while it increases currents in nickel, copper, and metal-free phthalocyanine sensors; oxidation and reduction of hydrogen peroxide via catalysis at the phthalocyanine surface are consistent with the pattern of sensor responses. This represents the first example of MPc vapor sensors being oxidized and reduced by the same analyte by varying the metal center. Consequently, differential analysis by redox contrast with catalytic amplification using a small array of sensors may be used to uniquely identify peroxide vapors. Metallophthalocyanine chemiresistors represent an improvement over existing peroxide vapor detection technologies in durability and selectivity in a greatly decreased package size.

Novel hybrid materials based on the vanadium oxide nanobelts

NASA Astrophysics Data System (ADS)

Zabrodina, G. S.; Makarov, S. G.; Kremlev, K. V.; Yunin, P. A.; Gusev, S. A.; Kaverin, B. S.; Kaverina, L. B.; Ketkov, S. Yu.

2016-04-01

Novel hybrid materials based on zinc phthalocyanine and nanostructured vanadium oxides have attracted extensive attention for the development of academic research and innovative industrial applications such as flexible electronics, optical sensors and heterogeneous catalysts. Vanadium oxides nanobelts were synthesized via a hydrothermal treatment V2O5·nH2O gel with surfactants (TBAB, CTAB) used as structure-directing agents, where CTAB - cetyltrimethylammonium bromide, TBAB - tetrabutylammonium bromide. Hybrid materials were prepared decoration of (CTA)0.33V2O5 flexible nanobelts with cationic zinc phthalocyanine by the ion-exchange route. Investigations of the thermal stability, morphologies and structures of the (CTA)0.33V2O5, (TBA)0.16V2O5 nanobelts and zinc phthalocyanine exchange product were carried out. The hybrid materials based on the nanostructured vanadium oxide and zinc phthalocyanine were tested as photocatalysts for oxidation of citronellol and 2-mercaptoethanol by dioxygen.

New metal phthalocyanines/metal simple hydroxide multilayers: experimental evidence of dipolar field-driven magnetic behavior.

PubMed

Bourzami, Riadh; Eyele-Mezui, Séraphin; Delahaye, Emilie; Drillon, Marc; Rabu, Pierre; Parizel, Nathalie; Choua, Sylvie; Turek, Philippe; Rogez, Guillaume

2014-01-21

A series of new hybrid multilayers has been synthesized by insertion-grafting of transition metal (Cu(II), Co(II), Ni(II), and Zn(II)) tetrasulfonato phthalocyanines between layers of Cu(II) and Co(II) simple hydroxides. The structural and spectroscopic investigations confirm the formation of new layered hybrid materials in which the phthalocyanines act as pillars between the inorganic layers. The magnetic investigations show that all copper hydroxide-based compounds behave similarly, presenting an overall antiferromagnetic behavior with no ordering down to 1.8 K. On the contrary, the cobalt hydroxide-based compounds present a ferrimagnetic ordering around 6 K, regardless of the nature of the metal phthalocyanine between the inorganic layers. The latter observation points to strictly dipolar interactions between the inorganic layers. The amplitude of the dipolar field has been evaluated from X-band and Q-band EPR spectroscopy investigation (Bdipolar ≈ 30 mT).

Comparison between the electrocatalytic properties of different metal ion phthalocyanines and porphyrins towards the oxidation of hydroxide.

PubMed

De Wael, Karolien; Adriaens, Annemie

2008-02-15

This work reports on the electrocatalytic oxidation of hydroxide using different central metal ion phthalocyanines and porphyrins immobilized on gold electrodes. The apparent electrocatalytic activity of cobalt phthalocyanine or porphyrin modified electrodes was found to be the greatest among the present series of metal ion macrocycles investigated. Copper and unmetallated phthalocyanine or porphyrin modified electrodes show no electrocatalytic behaviour towards hydroxide, such as bare gold. A possible mechanism for the enhanced reactivity of cobalt ion macrocycles towards the oxygen evolution is given. It is also stated that the electrocatalytic activity towards an adsorbate involves several aspects, such as the coordination state of the central metal ion, the nature of the ligand, the stability of the complexes, the number of d electrons, the energy of orbitals and the strength of the bonding between the central metal ion and the axial ligand.

Thermosetting Phthalocyanine Polymers

NASA Technical Reports Server (NTRS)

Fohlen, G.; Parker, J.; Achar, B.

1985-01-01

Group of phthalocyanine polymers resist thermal degradation. Polymers expected semiconducting. Principal applications probably in molded or laminated parts that have to withstand high temperatures. Polymers made from either of two classes of monomer: Bisphthalonitriles with imide linkages or Bisphthalonitriles with ester-imide linkages.

Conjugation of isoniazid to a zinc phthalocyanine via hydrazone linkage for pH-dependent liposomal controlled release

NASA Astrophysics Data System (ADS)

Nkanga, Christian Isalomboto; Krause, Rui Werner Maçedo

2018-05-01

Tuberculosis (TB) remains the leading cause of mortality from infectious diseases. Extended TB treatment and frequent adverse effects, due to poor bioavailability of anti-tubercular drugs (ATBDs), represent the main rationales behind liposomal encapsulation for controlled delivery. Liposomes have been reported as potential vehicles for targeted delivery of ATBDs due to their rapid uptake by macrophages, which are known as the main host cells for TB causative agent (Mycobacterium tuberculosis). Additionally, the need for controlled release of ATBDs arises because leakage is part of the key liposome challenges for hydrophilic compounds like isoniazid (INH). In this study, INH was conjugated to a highly hydrophobic photosensitizer, zinc (II) phthalocyanine (PC), through hydrazone bonding. The obtained conjugate (PC-INH) was encapsulated in liposomes by film hydration method. PC-INH loaded liposomes (PILs) were characterized using dynamic light scattering, transmission electron microscopy, energy-dispersive X-ray spectrometry and UV-Vis absorption spectrometry, which was used also for estimation of encapsulation efficiency (%EE). INH release was evaluated in different pH media using dialysis. Particle size, zeta potential and %EE of PILs were about 506 nm, - 55 mV and 72%, respectively. Over 12 h, PILs exhibited 22, 41, 97 and 100% of INH, respectively, released in pH 7.4, 6.4, 5.4 and 4.4 media. This pH-dependent behavior is attractive for site-specific delivery. These findings suggest the conjugation of chemotherapeutics to phthalocyanines using pH-labile linkages as a potential strategy for liposomal controlled release.

Ground and excited states of zinc phthalocyanine, zinc tetrabenzoporphyrin, and azaporphyrin analogs using DFT and TDDFT with Franck-Condon analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Theisen, Rebekah F., E-mail: rtheisen@asu.edu; Huang, Liang; Fleetham, Tyler

2015-03-07

The electronic structure of eight zinc-centered porphyrin macrocyclic molecules are investigated using density functional theory for ground-state properties, time-dependent density functional theory (TDDFT) for excited states, and Franck-Condon (FC) analysis for further characterization of the UV-vis spectrum. Symmetry breaking was utilized to find the lowest energy of the excited states for many states in the spectra. To confirm the theoretical modeling, the spectroscopic result from zinc phthalocyanine (ZnPc) is used to compare to the TDDFT and FC result. After confirmation of the modeling, five more planar molecules are investigated: zinc tetrabenzoporphyrin (ZnTBP), zinc tetrabenzomonoazaporphyrin (ZnTBMAP), zinc tetrabenzocisdiazaporphyrin (ZnTBcisDAP), zinc tetrabenzotransdiazaporphyrinmore » (ZnTBtransDAP), and zinc tetrabenzotriazaporphyrin (ZnTBTrAP). The two latter molecules are then compared to their phenylated sister molecules: zinc monophenyltetrabenzotriazaporphyrin (ZnMPTBTrAP) and zinc diphenyltetrabenzotransdiazaporphyrin (ZnDPTBtransDAP). The spectroscopic results from the synthesis of ZnMPTBTrAP and ZnDPTBtransDAP are then compared to their theoretical models and non-phenylated pairs. While the Franck-Condon results were not as illuminating for every B-band, the Q-band results were successful in all eight molecules, with a considerable amount of spectral analysis in the range of interest between 300 and 750 nm. The π-π{sup ∗} transitions are evident in the results for all of the Q bands, while satellite vibrations are also visible in the spectra. In particular, this investigation finds that, while ZnPc has a D{sub 4h} symmetry at ground state, a C{sub 4v} symmetry is predicted in the excited-state Q band region. The theoretical results for ZnPc found an excitation energy at the Q-band 0-0 transition of 1.88 eV in vacuum, which is in remarkable agreement with published gas-phase spectroscopy, as well as our own results of ZnPc in solution with Tetrahydrofuran that are provided in this paper.« less

Non-aqueous primary cell

NASA Astrophysics Data System (ADS)

James, S. D.; Smith, P. H.; Oneill, K. M.; Wilson, M. H.

1986-05-01

This patent application relates to electrochemical cells and especially to high-energy, liquid cathode, non-aqueous lithium electrochemical cells free from highly toxic materials. A non-aqueous lithium electrochemical cell is described which includes a halocarbon cathode depolarizer which is 1,2-dichloroethane, 1.1,2-trichloroethane, 1,1,2,2-tetrachloroethane, 1,2-dichloro-1,1-difluoroethane or mixtures thereof and a cathode catalyst which is copper, rhodium, palladium, cobalt phthalocyanine, nickel phthalocyanine, iron phthalocyanine, a cobalt tetraaza-(14)-annulene, a nickel tetraaza-(14)-annulene, a iron tetraaza-(14)-annulene, a cobalt porphyrin, a nickel porphyrin, a iron porphyrin, or a mixture thereof.

Phthalocyanine based metal containing porous carbon sheet

NASA Astrophysics Data System (ADS)

Honda, Z.; Sakaguchi, Y.; Tashiro, M.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

2017-03-01

Highly-ordered fused-ring poly copper phthalocyanine (PCuPc) was prepared using copper octacyanophthalocyanine as a building block, and two-dimensional (2D) square superlattices were directly observed by the transmission electron microscopy. Remarkably, we have found a formation of polymer network that consists of a 2D porous PCuPc sheet in which the centers of phthalocyanine units are alternately occupied by Cu atom and vacancy. Using this "half-filling" PCuPc, it must be possible to create alternating arrangements for transition metal centers, and therefore control the magnetic properties of the 2D carbon sheets.

Fabricating photoswitches and field-effect transistors from self-assembled tetra(2-isopropyl-5-methyphenoxy) copper phthalocyanines nanowires.

PubMed

Cheng, Chuanwei; Gao, Junshan; Xu, Guoyue; Zhang, Haiqian; Li, Yingying; Luo, Yan

2009-05-01

Tetra(2-isopropyl-5-methyphenoxy) copper phthalocyanine (CuPc) nanowires synthesized by a facile, low temperature self-assembled route, were incorporated into nano-devices: photoswitch and organic field-effect transistor. The devices were capable of switching on/off reversibly and fast by turning the 808 nm infrared light on/off. And the carrier mobility micro of CuPc nanowires incorporated in the devices was -0.02 cm2/V x s. The prelimenary results in this study show the potential application of metal phthalocyanine nanowires in low-cost fabrication of nano photo-electric devices.

Effect of pyridine on infrared absorption spectra of copper phthalocyanine.

PubMed

Singh, Sukhwinder; Tripathi, S K; Saini, G S S

2008-02-01

Infrared absorption spectra of copper phthalocyanine in KBr pellet and pyridine solution in 400-1625 and 2900-3200 cm(-1)regions are reported. In the IR spectra of solid sample, presence of weak bands, which are forbidden according to the selection rules of D4h point group, is explained on the basis of distortion in the copper phthalocyanine molecule caused by the crystal packing effects. Observation of a new band at 1511 cm(-1) and change in intensity of some other bands in pyridine are interpreted on the basis of coordination of the solvent molecule with the central copper ion.

Copper retention, calcium release and ultrastructural evidence indicate specific Cuprolinic Blue uptake and peculiar modifications in mineralizing aortic valves.

PubMed

Ortolani, F; Tubaro, F; Petrelli, L; Gandaglia, A; Spina, M; Marchini, M

2002-01-01

Previously, reactions with copper phthalocyanines at 0.05 M critical electrolyte concentration were found to cause demineralization in calcifying porcine aortic valves after subdermal implantation in rat, as well as simultaneous visualization of peculiar phthalocyanine-positive layers around cells and cell-derived matrix vesicles. In the present investigation, an appraisal was made of the mechanism and specificity of reactions with Cuprolinic Blue by comparing quantitatively calcium release and copper retention by calcified aortic valves reacted with this phthalocyanine under different critical electrolyte concentration conditions, and the corresponding ultrastructural patterns. It was found that (i) decalcifying properties are inversely proportional to salt molarity; (ii) reactivity to Cuprolinic Blue is critical electrolyte concentration-dependent, since the greatest copper retention occurred in 0.05 M critical electrolyte concentration Cuprolinic Blue-reacted samples, the only ones that also exhibited phthalocyanine-positive layers; (iii) the appearance of phthalocyanine-positive layers depends on Cuprolinic Blue uptake, revealing pericellular clustering of calcium-binding, anionic molecules; and (iv) minor Cuprolinic Blue uptake occurs by residual proteoglycans which still remain in the extracellular matrix after 6-week-long subdermal implantation. The present results indicate that this method is appropriate for the study of mineralized tissues and illustrate peculiar tissue modifications occurring at least in the experimental conditions used here.

Combination of hyperthermia and photodynamic therapy on mesenchymal stem cell line treated with chloroaluminum phthalocyanine magnetic-nanoemulsion

NASA Astrophysics Data System (ADS)

de Paula, Leonardo B.; Primo, Fernando L.; Pinto, Marcelo R.; Morais, Paulo C.; Tedesco, Antonio C.

2015-04-01

The present study reports on the preparation and the cell viability assay of two nanoemulsions loaded with magnetic nanoparticle and chloroaluminum phthalocyanine. The preparations contain equal amount of chloroaluminum phthalocyanine (0.05 mg/mL) but different contents of magnetic nanoparticle (0.15×1013 or 1.50×1013 particle/mL). The human bone marrow mesenchymal stem cell line was used as the model to assess the cell viability and this type of cell can be used as a model to mimic cancer stem cells. The cell viability assays were performed in isolated as well as under combined magnetic hyperthermia and photodynamic therapy treatments. We found from the cell viability assay that under the hyperthermia treatment (1 MHz and 40 Oe magnetic field amplitude) the cell viability reduction was about 10%, regardless the magnetic nanoparticle content within the magnetic nanoparticle/chloroaluminum phthalocyanine formulation. However, cell viability reduction of about 50% and 60% were found while applying the photodynamic therapy treatment using the magnetic nanoparticle/chloroaluminum phthalocyanine formulation containing 0.15×1013 or 1.50×1013 magnetic particle/mL, respectively. Finally, an average reduction in cell viability of about 66% was found while combining the hyperthermia and photodynamic therapy treatments.

Noncovalent functionalization of pristine CVD single-walled carbon nanotubes with 3d metal(II) phthalocyanines by adsorption from the gas phase

NASA Astrophysics Data System (ADS)

Basiuk, Vladimir A.; Flores-Sánchez, Laura J.; Meza-Laguna, Victor; Flores-Flores, José Ocotlán; Bucio-Galindo, Lauro; Puente-Lee, Iván; Basiuk, Elena V.

2018-04-01

Noncovalent hybrids of carbon nanotubes (CNTs) with phthalocyanines (Pcs) is a subject of growing research effort focused on the development of new efficient organic photovoltaic cells, heterogeneous catalysts, lithium batteries, gas sensors, field effect transistors, among other possible applications. The main advantage of using unsubstituted Pcs is their very moderate cost and easy commercial availability. Unfortunately, the deposition of unsubstituted Pcs onto CNT sidewalls via the traditional liquid-phase strategy proves to be very problematic due to an extremely poor solubility of Pcs. At the same time, unsubstituted free-base H2Pc ligand and many of its transition metal complexes exhibit high thermal stability and volatility under reduced pressure, which allows for their physical vapor deposition onto solid surfaces. In the present work, we demonstrated the possibility of simple, fast, efficient and environmentally friendly noncovalent functionalization of single-walled CNTs (SWNTs) with a series of 3d metal(II) phthalocyanines Me(II)Pc, where Me = Co, Ni, Cu and Zn. The functionalization can be performed at 400-500 °C under moderate vacuum, and takes about 2-3 h only. The nanohybrids obtained were characterized by means of Fourier-transform infrared, Raman, UV-vis and energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), scanning and transmission electron microscopy. TGA suggested that Pc weight content is 30%, 17% and 35% for NiPc, CuPc and ZnPc, respectively (CoPc exhibited anomalous behavior), which is close to the estimates from EDS spectra of 24-39%, 27-36% and 27-44% for CoPc, CuPc and ZnPc, respectively. A strong increase in intensity of D band in the Raman spectra of SWNT‒Pc hybrids, as compared to that of pristine nanotubes, was interpreted as very strong interactions between Pc molecules and SWNT sidewalls. Very high absolute values of binding energies of 32.46-37.12 kcal/mol and the patterns of HOMO and LUMO distribution, calculated at the PBE-D/DNP level of density functional theory, also suggested that the interactions between metal phthalocyanines studied and nanotube sidewalls are very strong.

21 CFR 178.3297 - Colorants for polymers.

Code of Federal Regulations, 2010 CFR

2010-04-01

... finished articles are to contact food only under conditions of use D, E, F, and G. Phthalocyanine blue (C.I. pigment blue 15, 15:1, 15:2, 15:3, and 15:4; C.I. No. 74160; CAS Reg. No. 147-14-8) Phthalocyanine green...

21 CFR 178.3297 - Colorants for polymers.

Code of Federal Regulations, 2011 CFR

2011-04-01

... finished articles are to contact food only under conditions of use D, E, F, and G. Phthalocyanine blue (C.I. pigment blue 15, 15:1, 15:2, 15:3, and 15:4; C.I. No. 74160; CAS Reg. No. 147-14-8) Phthalocyanine green...

Recent Studies in Phthalocyanine Chemistry.

DTIC Science & Technology

1986-07-01

desulfurisation ) etc. Many of the uses cited In the preceding sentence involve a redox process in which two or more electrons are exchanged per reaction...phthalocyanine as a catalyst for desulfurisation of residues, effluents etc 144]. Acknowledgmnts We ars Indebted to the Natural Sciences and Engineering

Application of Raman microscopy to biodegradable double-walled microspheres.

PubMed

Widjaja, Effendi; Lee, Wei Li; Loo, Say Chye Joachim

2010-02-15

Raman mapping measurements were performed on the cross section of the ternary-phase biodegradable double-walled microsphere (DWMS) of poly(D,L-lactide-co-glycolide) (50:50) (PLGA), poly(L-lactide) (PLLA), and poly(epsilon-caprolactone) (PCL), which was fabricated by a one-step solvent evaporation method. The collected Raman spectra were subjected to a band-target entropy minimization (BTEM) algorithm in order to reconstruct the pure component spectra of the species observed in this sample. Seven pure component spectral estimates were recovered, and their spatial distributions within DWMS were determined. The first three spectral estimates were identified as PLLA, PLGA 50:50, and PCL, which were the main components in DWMS. The last four spectral estimates were identified as semicrystalline polyglycolic acid (PGA), dichloromethane (DCM), copper-phthalocyanine blue, and calcite, which were the minor components in DWMS. PGA was the decomposition product of PLGA. DCM was the solvent used in DWMS fabrication. Copper-phthalocyanine blue and calcite were the unexpected contaminants. The current result showed that combined Raman microscopy and BTEM analysis can provide a sensitive characterization tool to DWMS, as it can give more specific information on the chemical species present as well as the spatial distributions. This novel analytical method for microsphere characterization can serve as a complementary tool to other more established analytical techniques, such as scanning electron microscopy and optical microscopy.

Thermal Annealing Effect on Poly(3-hexylthiophene): Fullerene:Copper-Phthalocyanine Ternary Photoactive Layer

PubMed Central

Derouiche, H.; Mohamed, A. B.

2013-01-01

We have fabricated poly(3-hexylthiophene) (P3HT)/copper phthalocyanine (CuPc)/fullerene (C60) ternary blend films. This photoactive layer is sandwiched between an indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT/PSS) photoanode and a bathocuproine (BCP)/aluminium photocathode. The thin films have been characterized by atomic force microscope (AFM) and ultraviolet/visible spectroscopy in order to study the influence of P3HT doping on the morphological and optical properties of the photoactive layer. We have also compared the I-V characteristics of three different organic solar cells: ITO/PEDOT:PSS/CuPc0.5:C600.5/BCP/Al and ITO/PEDOT:PSS/P3HT0.3:CuPc0.3:C600.4/BCP/Al with and without annealing. Both structures show good photovoltaic behaviour. Indeed, the incorporation of P3HT into CuPc:C60 thin film improves all the photovoltaic characteristics. We have also seen that thermal annealing significantly improves the optical absorption ability and stabilizes the organic solar cells making it more robust to chemical degradation. PMID:23766722

Semiconducting polymers for gas detection

NASA Technical Reports Server (NTRS)

Byrd, N. R.; Sheratte, M. B.

1975-01-01

Conjugated polyenes, and polyesters containing phthalocyanine in their backbone, were synthesized. These polymers were characterized by chemical analysis, thermogravimetric analysis, spectral analysis, and X-ray diffraction studies for crystallinity, as well as for their film-forming capability and gas/polymer interactions. Most of the polymers were relatively insensitive to water vapor up to 50 percent relative humidity, but the polyester/phthalocyanine (iron) polymer was relatively insensitive up to 100 percent RH. On the other hand, poly(p-dimethylaminophenylacetylene) was too conductive at 100 percent RH. Of the gases tested, the only ones that gave any evidence of interacting with the polymers were SO2, NOx, HCN and NH3. Poly(imidazole)/thiophene responded to each of these gases at all relative humidities, while the other polymers gave varying response, depending upon the RH. Thus, since most of these gases were electron-accepting, the electron-donating character of poly(imidazole)/thiophene substantiates the concept of electronegativity being the operating principle for interaction effects. Of the six polymers prepared, poly(imidazole)/thiophene first showed a very good response to smoldering cotton, but it later became nonresponsive; presumably due to oxidation effects.

Thermal annealing effect on poly(3-hexylthiophene): fullerene:copper-phthalocyanine ternary photoactive layer.

PubMed

Derouiche, H; Mohamed, A B

2013-01-01

We have fabricated poly(3-hexylthiophene) (P3HT)/copper phthalocyanine (CuPc)/fullerene (C60) ternary blend films. This photoactive layer is sandwiched between an indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT/PSS) photoanode and a bathocuproine (BCP)/aluminium photocathode. The thin films have been characterized by atomic force microscope (AFM) and ultraviolet/visible spectroscopy in order to study the influence of P3HT doping on the morphological and optical properties of the photoactive layer. We have also compared the I-V characteristics of three different organic solar cells: ITO/PEDOT:PSS/CuPc₀.₅:C60₀.₅/BCP/Al and ITO/PEDOT:PSS/P3HT₀.₃:CuPc₀.₃:C60₀.₄/BCP/Al with and without annealing. Both structures show good photovoltaic behaviour. Indeed, the incorporation of P3HT into CuPc:C60 thin film improves all the photovoltaic characteristics. We have also seen that thermal annealing significantly improves the optical absorption ability and stabilizes the organic solar cells making it more robust to chemical degradation.

Ultrafast studies of the excited-state dynamics of copper and nickel phthalocyanine tetrasulfonates: potential sensitizers for the two-photon photodynamic therapy of tumors.

PubMed

Fournier, Michel; Pépin, Claude; Houde, Daniel; Ouellet, René; van Lier, Johan E

2004-01-01

In order to evaluate the potential of copper and nickel phthalocyanine tetrasulfonates as sensitizers for two-photon photodynamic therapy, we conducted kinetic femtosecond measurements of transient absorption and bleaching of their excited state dynamics in aqueous solution. Samples were pumped with 620 nm and 310 nm laser light, which allowed us to study relaxation processes from both the first and second singlet (or doublet for the copper phthalocyanine) excited states. A second excitation from the first excited triplet state, approximately 685 and 105 ps after the first excitation for copper and nickel phthalocyanine tetrasulfonate respectively, was the most efficient way to bring the molecules to an upper triplet state. Presumably this highest triplet state can inflict molecular damage on adjacent biomolecules int eh absence of oxygen, resulting in the desired cytotoxic cellular response. Transient absorption spectra at different fixed delays indicate that optimum efficiency would require that the second photon has a wavelength of approximately 750 nm.

Inverted methoxypyridinium phthalocyanines for PDI of pathogenic bacteria.

PubMed

Lourenço, Leandro M O; Sousa, Andreina; Gomes, Maria C; Faustino, Maria A F; Almeida, Adelaide; Silva, Artur M S; Neves, Maria G P M S; Cavaleiro, José A S; Cunha, Ângela; Tomé, João P C

2015-10-01

Phthalocyanines (Pc) are photoactive molecules that can absorb and emit light in a large range of the UV-Vis spectrum with recognized potential for medical applications. Considering the biomedical applications an important limitation of these compounds is their low solubility in water. The use of suitable pyridinium groups on Pc is a good strategy to solve this drawback and to make them more effective to photoinactivate Gram-negative bacteria via a photodynamic inactivation (PDI) approach. Herein, an easy synthetic access to obtain inverted tetra- and octa-methoxypyridinium phthalocyanines (compounds 5 and 6) and also their efficiency to photoinactivate a recombinant bioluminescent strain of Escherichia coli is described. The obtained results were compared with the ones obtained when more conventional thiopyridinium phthalocyanines (compounds 7 and 8) were used. This innovative study comparing thiopyridinium and inverted methoxypyridinium moieties on cationic Pc is reported for the first time taking into account the efficiency of singlet oxygen ((1)O2) generation, water solubility and uptake properties.

Effect of axial ligands on the molecular configurations, stability, reactivity, and photodynamic activities of silicon phthalocyanines.

PubMed

Luan, Liqiang; Ding, Lanlan; Shi, Jiawei; Fang, Wenjuan; Ni, Yuxing; Liu, Wei

2014-12-01

To demonstrate the effect of axial ligands on the structure-activity relationship, a series of axially substituted silicon phthalocyanines (SiPcs) have been synthesized with changes to the axial ligands. The reactivity of the axial ligand upon shielding by the phthalocyanine ring current, along with their stability, photophysical, and photodynamic therapy (PDT) activities were compared and evaluated for the first time. As revealed by single-crystal XRD analysis, rotation of the axial -OMe ligands was observed in SiPc 3, which resulted in two molecular configurations coexisting synchronously in both the solid and solution states and causing a split of the phthalocyanine α protons in the (1)H NMR spectra that is significantly different from all SiPcs reported so far. The remarkable photostability, good singlet oxygen quantum yield, and efficient in vitro photodynamic activity synergistically show that compound 3 is one of the most promising photosensitizers for PDT. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic investigation of different concentrations of the vapour deposited copper phthalocyanine as a "guest" in polyimide matrix.

PubMed

Georgiev, Anton; Yordanov, Dancho; Dimov, Dean; Assa, Jacob; Spassova, Erinche; Danev, Gencho

2015-04-05

Nanocomposite layers 250 nm copper phthalocyanine/polyimide prepared by simultaneous vapour deposition of three different sources were studied. Different concentrations of copper phthalocyanine as a "guest" in polyimide matrix as a function of conditions of the preparation have been determined by FTIR (Fourier Transform Infrared) and UV-VIS (Ultraviolet-Visible) spectroscopies. The aim was to estimate the possibility of the spectroscopic methods for quantitative determination of the "guest" and compare with the quality of the polyimide thin films in relation to the "guest" concentration. The band at 1334 cm(-1) has been used for quantitative estimation of "guest" in polyimide matrix. The concentrations of the copper phthalocyanine less than 20% require curve fitting techniques with Fourier self deconvolution. The relationship between "guest" concentrations and degree of imidization, as well as the electronic UV-VIS spectra are discussed in relation to the composition, imidization degree and the two crystallographic modification of the embedded chromophore. Copyright © 2015 Elsevier B.V. All rights reserved.

Pentalysine β-Carbonylphthalocyanine Zinc: An Effective Tumor-Targeting Photosensitizer for Photodynamic Therapy

PubMed Central

Chen, Zhuo; Zhou, Shanyong; Chen, Jincan; Deng, Yicai; Luo, Zhipu; Chen, Hongwei; Hamblin, Michael R.

2010-01-01

Unsymmetrical phthalocyanine derivatives have been widely studied as photosensitizers for photodynamic therapy (PDT), targeting various tumor types. However, the preparation of unsymmetrical phthalocyanines is always a challenge due to the presence of many possible structural isomers. Herein we report a new unsymmetrical zinc phthalocyanine, pentalysine β-carbonylphthalocyanine zinc (ZnPc-(Lys)5), that was prepared in large quantity and high purity. This is a water-soluble cationic photosensitizer and maintains a high quantum yield of singlet oxygen generation similar to that of unsubstituted zinc phthalocyanine (ZnPc). Compared with anionic ZnPc counterparts, ZnPc-(Lys)5 shows a higher level cellular uptake and 20-fold higher phototoxicity toward tumor cells. Pharmacokinetics and PDT studies of ZnPc-(Lys)5 in S180 tumor-bearing mice showed a high ratio of tumor versus skin retention and significant tumor inhibition. This new molecular framework will allow synthetic diversity in the number of lysine residues incorporated and will facilitate future QSAR studies. PMID:20458713

Oncologic photodynamic diagnosis and therapy: confocal Raman/fluorescence imaging of metal phthalocyanines in human breast cancer tissue in vitro.

PubMed

Abramczyk, Halina; Brozek-Pluska, Beata; Surmacki, Jakub; Musial, Jacek; Kordek, Radzislaw

2014-11-07

Raman microspectroscopy and confocal Raman imaging combined with confocal fluorescence were used to study the distribution and aggregation of aluminum tetrasulfonated phthalocyanine (AlPcS4) in noncancerous and cancerous breast tissues. The results demonstrate the ability of Raman spectroscopy to distinguish between noncancerous and cancerous human breast tissue and to identify differences in the distribution and aggregation of aluminum phthalocyanine, which is a potential photosensitizer in photodynamic therapy (PDT), photodynamic diagnosis (PDD) and photoimmunotherapy (PIT) of cancer. We have observed that the distribution of aluminum tetrasulfonated phthalocyanine confined in cancerous tissue is markedly different from that in noncancerous tissue. We have concluded that Raman imaging can be treated as a new and powerful technique useful in cancer photodynamic therapy, increasing our understanding of the mechanisms and efficiency of photosensitizers by better monitoring localization in cancer cells as well as the clinical assessment of the therapeutic effects of PDT and PIT.

Gas Sensing Properties of bis-Phthalocyanine Thin Film

NASA Astrophysics Data System (ADS)

Dumludag, Fatih; Kilic, Pinar; Odabas, Zafer; Altindal, Ahmet; Bekaroglu, Ozer

2010-01-01

In this study, response of the cofacial bis- phthalocyanine film to vapor of Volatile Organic Compounds (VOCs) was investigated. Test gases were vapors of acetone, toluene, ethanol and ammonia. Measurements were carried out between the temperatures of 293 K-423 K. Bis-phthalocyanine was dissolved in chloroform. Thin film of bis-phthalocyanine was deposited by spraying method on glass substrate patterned with Interdigital Transducer (IDT). During the measurements 0.5 volts were applied to the IDT. Response characteristics of the film were determined by means of change in dc conductivity as a function of gas concentration and temperature. Gas concentrations were controlled by mass flow controller. Dry nitrogen was used as carrier gas. Vapor pressure of the VOCs was calculated using Antoine equation. Response characteristics of the film were determined in a wide range of gas concentration (0.25%-18%). The film showed good sensitivity to the VOCs vapors in the measurement range. The responses of the film were reversible. All the measurement system was computerized.

Self-assembled nanostructures of optically active phthalocyanine derivatives. Effect of central metal ion on the morphology, dimension, and handedness.

PubMed

Sun, Ranran; Wang, Liang; Tian, Jing; Zhang, Xiaomei; Jiang, Jianzhuang

2012-11-21

Four optically active {(2,3,9,10,16,17,23,24-octa[(S)-2-methylbutoxy]} phthalocyanine derivatives with different central metal ions, namely (S)-H2Pc(β-OC5H11)8 (1), (S)-ZnPc(β-OC5H11)8 (2), (S)-CuPc(β-OC5H11)8 (3), and (S)-NiPc(β-OC5H11)8 (4) have been synthesized and their self-assembly behaviors systematically investigated by electronic absorption and circular dichroism (CD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) techniques, and X-ray photoelectron spectroscopy (XPS). Metal free phthalocyanine together with its zinc and copper congeners self-assembles into right-handed helical arrangements in a stack of phthalocyanine chromophores according to the CD spectroscopic result, while the nickel complex does so into the left-handed helical arrangements. These helical arrangements, acting as elemental primary structures, further pack in a hierarchical fashion into either highly ordered right-handed fibrous nanostructures with average 300 μm length, 4.8 μm width, and 4.4 μm helical pitch for 1 and 300 μm length, 2.4 μm width, and 1.8 μm helical pitch for 2 but left-handed fibrous nanostructures with average 4 μm length, 0.48 μm width, and 0.12 μm helical pitch for 3 and 300 μm length, 2 μm width, and 1.2 μm helical pitch for 4, clearly revealing the effect of central metal ion on the distance and relative orientation of neighboring phthalocyanine chromophores and in turn the supramolecular chirality, morphology, dimension, and handedness of the self-assembled nanostructures. The present result not only represents a unique phenomenon in the self-assembly of phthalocyanine compounds but more importantly denotes the transcription and amplification of molecular chirality to supramolecular helicity with different helical bias during the self-assembly processes without changing the chiral handles attached to the phthalocyanine chromophore.

Spectroscopic investigation of sulfonate phthalocyanine to probe enzyme reactions for heavy metals detection.

PubMed

Chaure, Shweta; Paul, Deepen; Vadagma, Pankaj; Ray, Asim K

2010-01-15

Optical absorption and Raman spectra of the sulfonated copper phthalocyanine (CuTsPc) layer were exploited for detection of cadmium (Cd) contaminants in water. Acetylcholine esterase was immobilized by freely suspending them in calcium alginate microbeads and this gel was then spincoated on the drop cast sulfonated copper phthalocyanine film on a glass substrate to form a bilayer. The inhibition of catalytic reaction between acetylcholine chloride and enzyme due to Cd contaminants was monitored by recording changes in spectra of drop cast CuTsPc as an indicator. The detection limit of cadmium content in water was found to be 1 ppm.

Application of nanophotosensitizers (aluminum phthalocyanine nanoparticles) for early diagnosis and prevention of inflammatory diseases

NASA Astrophysics Data System (ADS)

Kuznetsova, J. O.; Makarov, V. I.

2016-08-01

This paper deals with a possibility of new types of photosensitizers application - Aluminum Phthalocyanine nanoparticles (nAlPc) in clinical practice for diagnosis, prevention and therapy of inflammatory diseases in dentistry and traumatology. It was detected that the aluminum phthalocyanine (AlPc) fluoresces in the nanoparticle form in the presence of pathologic microflora or inflammation process. It will make possible to detect the local accumulation of pathological microflora on the enamel surface and also for diagnostics and treatment of inflammatory diseases. Experimental studies of interaction of NP-AlPc with tooth enamel and with biological joint tissue at arthrosis are presented.

Changes in the Spectral Features of Zinc Phthalocyanine Induced by Nitrogen Dioxide Gas in Solution and in Solid Polymer Nanofiber Media.

PubMed

Zugle, Ruphino; Tetteh, Samuel

2017-03-01

The changes in the spectral features of zinc phthalocyanine in the visible domain as a result of its interaction with nitrogen dioxide gas were assessed in this work. This was done both in solution and when the phthalocyanine was incorporated into a solid polystyrene polymer nanofiber matrix. The spectral changes were found to be spontaneous and marked in both cases suggesting a rapid response criterion for the detection of the gas. In particular, the functionalised nano-fabric material could serve as a practical fire alarm system as it rapidly detects the nitrogen dioxide gas generated during burning.

Metal (2) 4,4',4",4'" phthalocyanine tetraamines as curing agents for epoxy resins

NASA Technical Reports Server (NTRS)

Achar, B. N.; Fohlen, G. M.; Parker, J. A. (Inventor)

1985-01-01

Metal, preferably divalent copper, cobalt or nickel, phthalocyanine tetraamines are used as curing agents for epoxides. The resulting copolymers have high thermal and chemical resistance and are homogeneous. They are useful as binders for laminates, e.g., graphite cloth laminate.

Molecular Electronic Devices Based On Electrooptical Behavior Of Heme-Like Molecules

NASA Astrophysics Data System (ADS)

Simic-Glavaski, B.

1986-02-01

This paper discusses application of the electrically modulated and unusually strong Raman emitted light produced by an adsorbed monolayer of phthalocyanine molecules on silver electrode or silver bromide substrates and on neural membranes. The analysis of electronic energy levels in semiconducting silver bromide and the adsorbed phthalocyanine molecules suggests a lasing mechanism as a possible origin of the high enhancement factor in surface enhanced Raman scattering. Electrically modulated Raman scattering may be used as a carrier of information which is drawn fran the fast intramolecular electron transfer aN,the multiplicity of quantum wells in phthalocyanine molecules. Fast switching times on the order of 10-13 seconds have been measured at room temperature. Multilevel and multioutput optical signals have also been obtained fran such an electrically modulated adsorbed monolayer of phthalocyanine molecules which can be precisely addressed and interrogated. This may be of practical use to develop Nlecular electronic devices with high density memory and fast parallel processing systems with a typical 1020 gate Hz/cm2 capacity at room temperature for use in optical computers. The paper also discusses the electrooptical modulation of Raman signals obtained from adsorbed bio-compatible phthalocyanine molecules on nerve membranes. This optical probe of neural systems can be used in studies of complex information processing in neural nets and provides a possible method for interfacing natural and man-made information processing devices.

Excited-State Deactivation of Branched Phthalocyanine Compounds.

PubMed

Zhu, Huaning; Li, Yang; Chen, Jun; Zhou, Meng; Niu, Yingli; Zhang, Xinxing; Guo, Qianjin; Wang, Shuangqing; Yang, Guoqiang; Xia, Andong

2015-12-21

The excited-state relaxation dynamics and chromophore interactions in two phthalocyanine compounds (bis- and trisphthalocyanines) are studied by using steady-state and femtosecond transient absorption spectral measurements, where the excited-state energy-transfer mechanism is explored. By exciting phthalocyanine compounds to their second electronically excited states and probing the subsequent relaxation dynamics, a multitude of deactivation pathways are identified. The transient absorption spectra show the relaxation pathway from the exciton state to excimer state and then back to the ground state in bisphthalocyanine (bis-Pc). In trisphthalocyanine (tris-Pc), the monomeric and dimeric subunits are excited and the excitation energy transfers from the monomeric vibrationally hot S1 state to the exciton state of a pre-associated dimer, with subsequent relaxation to the ground state through the excimer state. The theoretical calculations and steady-state spectra also show a face-to-face conformation in bis-Pc, whereas in tris-Pc, two of the three phthalocyanine branches form a pre-associated face-to-face dimeric conformation with the third one acting as a monomeric unit; this is consistent with the results of the transient absorption experiments from the perspective of molecular structure. The detailed structure-property relationships in phthalocyanine compounds is useful for exploring the function of molecular aggregates in energy migration of natural photosynthesis systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-dimensional artificial light-harvesting antennae with predesigned high-order structure and robust photosensitising activity

PubMed Central

Feng, Xiao; Ding, Xuesong; Chen, Long; Wu, Yang; Liu, Lili; Addicoat, Matthew; Irle, Stephan; Dong, Yuping; Jiang, Donglin

2016-01-01

Highly ordered discrete assemblies of chlorophylls that are found in natural light-harvesting antennae are key to photosynthesis, which converts light energy to chemical energy and is the principal producer of organic matter on Earth. Porphyrins and phthalocyanines, which are analogues of chlorophylls, exhibit a strong absorbance of visible and near-infrared light, respectively. A highly ordered porphyrin-co-phthalocyanine antennae would harvest photons over the entire solar spectrum for chemical transformation. However, such a robust antennae has not yet been synthesised. Herein, we report a strategy that merges covalent bonds and noncovalent forces to produce highly ordered two-dimensional porphyrin-co-phthalocyanine antennae. This methodology enables control over the stoichiometry and order of the porphyrin and phthalocyanine units; more importantly, this approach is compatible with various metalloporphyrin and metallophthalocyanine derivatives and thus may lead to the generation of a broad structural diversity of two-dimensional artificial antennae. These ordered porphyrin-co-phthalocyanine two-dimensional antennae exhibit unique optical properties and catalytic functions that are not available with single-component or non-structured materials. These 2D artificial antennae exhibit exceptional light-harvesting capacity over the entire solar spectrum as a result of a synergistic light-absorption effect. In addition, they exhibit outstanding photosensitising activities in using both visible and near-infrared photons for producing singlet oxygen. PMID:27622274

Nanostructured hybrid ZnO thin films for energy conversion

PubMed Central

2011-01-01

We report on hybrid films based on ZnO/organic dye prepared by electrodeposition using tetrasulfonated copper phthalocyanines (TS-CuPc) and Eosin-Y (EoY). Both the morphology and porosity of hybrid ZnO films are highly dependent on the type of dyes used in the synthesis. High photosensitivity was observed for ZnO/EoY films, while a very weak photoresponse was obtained for ZnO/TS-CuPc films. Despite a higher absorption coefficient of TS-CuPc than EoY, in ZnO/EoY hybrid films, the excited photoelectrons between the EoY levels can be extracted through ZnO, and the porosity of ZnO/EoY can also be controlled. PMID:21711909

Fabrication and characterization of the organic rectifying junctions by electrolysis

NASA Astrophysics Data System (ADS)

Karimov, Khasan; Ahmad, Zubair; Ali, Rashid; Noor, Adnan; Akmal, M.; Najeeb, M. A.; Shakoor, R. A.

2017-08-01

Unlike the conventional solution processable deposition techniques, in this study, we propose a novel and economical method for the fabrication of organic rectifying junctions. The solutions of the orange dye, copper phthalocyanine and NaCl were deposited on the surface-type interdigitated silver electrodes using electrolysis technique. Using the current-voltage (I-V) characteristics, the presence of rectifying behavior in the samples has been confirmed. This phenomenon, in principle, can be used for fabrication of the diodes, transistors and memory devices.

Development and evaluation of zinc phthalocyanine nanoemulsions for use in photodynamic therapy for Leishmania spp.

NASA Astrophysics Data System (ADS)

Betzler de Oliveira de Siqueira, Luciana; da Silva Cardoso, Verônica; Almeida Rodrigues, Igor; Lúcia Vazquez-Villa, Ana; Pereira dos Santos, Elisabete; da Costa Leal Ribeiro Guimarães, Bruno; dos Santos Cerqueira Coutinho, Cristal; Vermelho, Alane Beatriz; Ricci Junior, Eduardo

2017-02-01

Photodynamic therapy (PDT) combines light with photosensitizers (PS) for production of reactive oxygen species (ROS) that can kill infectious microorganisms such as bacteria, fungi and protozoa. The application of nanotechnology has enabled the advancement of PDT because many PS are insoluble in water, necessitating a nanocarrier as a physiologically acceptable carrier. Nanoemulsions are efficient nanocarriers for solubilizing liposoluble drugs, like the PS, in water. Cutaneous (CL) and mucocutaneous leishmaniasis (ML) are caused by different species of the genus Leishmania, transmitted to humans by sandfly bites. Parasites are hosted in skin macrophages producing ulcerative lesions. Thus, a topical treatment, effective and inexpensive, for CL and ML is preferable to systemic interventions. There are topical treatments like paromomycin and amphotericin B, but they have many local side effects or a very high cost, limiting their use. This work aimed to develop a zinc phthalocyanine (photosensitizer) oil-in-water nanoemulsion, essential clove oil and polymeric surfactant (Pluronic® F127) for the formulation of a topical delivery system for use in PDT against Leishmania amazonensis and Leishmania infantum. The nanoemulsion was produced by a high-energy method and characterized by size, polydispersity, morphology, pH, content and stability studies. The toxicity in the dark and the photobiological activity of the formulations were evaluated in vitro for Leishmania and macrophages. The formulation presented was pH compatible with topical use, approximately 30 nm in size, with a polydispersity index ≤0.1 and remained stable at room and refrigerator temperature during the stability study (60 days). The zinc phthalocyanine nanoemulsion is effective in PDT against Leishmania spp.; use against skin infections can be a future application of this topical formulation, avoiding the use of oral or injectable medications, decreasing systemic adverse effects.

Dianionic Titanyl and Vanadyl (Cation+ )2 [MIV O(Pc4- )]2- Phthalocyanine Salts Containing Pc4- Macrocycles.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Khasanov, Salavat S; Litvinov, Alexey L; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

2018-06-18

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu 4 N + ) 2 [M IV O(Pc 4- )] 2- (M=Ti, V) and (Bu 3 MeP + ) 2 [M IV O(Pc 4- )] 2- (M=Ti, V) with [M IV O(Pc 4- )] 2- dianions were synthesized and characterized. Reduction of M IV O(Pc 2- ) carried out with an excess of sodium fluorenone ketyl in the presence of Bu 4 N + or Bu 3 MeP + is exclusive to the phthalocyanine centers, forming Pc 4- species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C-N(pyr) bonds to elongate and the C-N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn-Teller effects are significant in the [eg(π*)] 2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when M IV O(Pc 2- ) was reduced to [M IV O(Pc . 3- )] . - and [M IV O(Pc 4- )] 2- . From magnetic measurements, [Ti IV O(Pc 4- )] 2- was found to be diamagnetic and (Bu 4 N + ) 2 [V IV O(Pc 4- )] 2- and (Bu 3 MeP + ) 2 [V IV O(Pc 4- )] 2- were found to have magnetic moments of 1.72-1.78 μ B corresponding to an S=1/2 spin state owing to V IV electron spin. As a result, two latter salts show EPR signals with V IV hyperfine coupling. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Reverse Saturable Absorption and Optical Limiting in Heavy-Atom Substituted Phthalocyanines

NASA Technical Reports Server (NTRS)

Perry, J. W.; Mansour, K.; Marder, S. R.; Alvarez, D., Jr.; Perry, K. J.; Choong, I.

1994-01-01

The reverse saturable absorption and optical limiting response of metal phthalocyaninies can be enhanced by using the heavy-atom effect. Phthalocyanines containing heavy metal atoms, such as In, Sn, and Pb show nearly a factor of two enhancement in the ratio of effective excited-state to ground-state absorption cross sections compared to those containing lighter atoms, such as Al and Si. In an f/8 optical geometry, homogeneous solutions of heavy metal phthalocyanines, at 30% linear transmission, limit 8-ns, 532-nm laser pulses to less than or equal to 3 (micro)J (the energy for 50% probability of eye damage) for incident pulses up to 800 (micro)J.

Metal-phthalocyanine functionalized carbon nanotubes as catalyst for the oxygen reduction reaction: A theoretical study

NASA Astrophysics Data System (ADS)

Orellana, Walter

2012-07-01

The covalent functionalization of metallic single-walled carbon nanotubes (CNTs) with transition metal phthalocyanines (MPc, with M = Mn, Fe and Co) are addressed by density functional calculations. The CNT-MPc catalytic activity toward the oxygen reduction reaction (ORR) is investigated through the O2 stretching frequency adsorbed on the phthalocyanine metal center. We find better reduction abilities when the CNT functionalization occurs through sp2-like bonds. Multiple stable-spin states for the M-O2 adduct are also found for M = Mn and Fe, suggesting higher ORR rates. The CNT-MPc complexes show metallic characteristics, suggesting favorable conditions to work as ORR cathode catalysts in fuel cells.

Facile one-pot preparation of thermally and photochemically convertible soluble precursors of copper phthalocyanine and naphthalocyanine.

PubMed

Kikukawa, Yuu; Fukuda, Takamitsu; Fuyuhiro, Akira; Ishikawa, Naoto; Kobayashi, Nagao

2011-08-14

Soluble copper phthalocyanine (CuPc) and naphthalocyanine (CuNc) precursors which can be converted thermally and photochemically into insoluble CuPc and CuNc, respectively, have been synthesized by a one-step reaction using commercially available chemicals. This journal is © The Royal Society of Chemistry 2011

Magnetic anisotropy of metal functionalized phthalocyanine 2D networks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Guojun; Zhang, Yun; Xiao, Huaping, E-mail: hpxiao@xtu.edu.cn

2016-06-15

The magnetic anisotropy of metal including Cr, Mn, Fe, Co, Mo, Tc, Ru, Rh, W, Re, Os, Ir atoms functionalized phthalocyanine networks have been investigated with first-principles calculations. The magnetic moments can be expressed as 8-n μ{sub B} with n the electronic number of outmost d shell in the transition metals. The huge magnetocrystalline anisotropy energy (MAE) is obtained by torque method. Especially, the MAE of Re functionalized phthalocyanine network is about 20 meV with an easy axis perpendicular to the plane of phthalocyanine network. The MAE is further manipulated by applying the external biaxial strain. It is found thatmore » the MAE is linear increasing with the external strain in the range of −2% to 2%. Our results indicate an effective approach to modulate the MAE for practical application. - Graphical abstract: The charge density redistribution (ρ{sub MPc}-ρ{sub M}-ρ{sub Pc}) and spin density of the CoPc molecule, from top- and side-views. Purple and green isosurfaces indicate charge depletion and accumulation, respectively. Display Omitted.« less

Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Massimi, Lorenzo, E-mail: lorenzo.massimi@uniroma1.it; Angelucci, Marco; Gargiani, Pierluigi

2014-06-28

Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption,more » and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.« less

Controlling Morphology and Molecular Packing of Alkane Substituted Phthalocyanine Blend Bulk Heterojunction Solar Cells†

PubMed Central

Jurow, Matthew J.; Hageman, Brian A.; Nam, Chang-Yong; Pabon, Cesar; Black, Charles T.

2013-01-01

Systematic changes in the exocyclic substiution of core phthalocyanine platform tune the absorption properties to yield commercially viable dyes that function as the primary light absorbers in organic bulk heterojunction solar cells. Blends of these complementary phthalocyanines absorb a broader portion of the solar spectrum compared to a single dye, thereby increasing solar cell performance. We correlate grazing incidence small angle x-ray scattering structural data with solar cell performance to elucidate the role of nanomorphology of active layers composed of blends of phthalocyanines and a fullerene derivative. A highly reproducible device architecture is used to assure accuracy and is relevant to films for solar windows in urban settings. We demonstrate that the number and structure of the exocyclic motifs dictate phase formation, hierarchical organization, and nanostructure, thus can be employed to tailor active layer morphology to enhance exciton dissociation and charge collection efficiencies in the photovoltaic devices. These studies reveal that disordered films make better solar cells, short alkanes increase the optical density of the active layer, and branched alkanes inhibit unproductive homogeneous molecular alignment. PMID:23589766

Enhanced Charge Separation Efficiency in Pyridine-Anchored Phthalocyanine-Sensitized Solar Cells by Linker Elongation.

PubMed

Ikeuchi, Takuro; Agrawal, Saurabh; Ezoe, Masayuki; Mori, Shogo; Kimura, Mutsumi

2015-11-01

A series of zinc phthalocyanine sensitizers (PcS22-24) having a pyridine anchoring group are designed and synthesized to investigate the structural dependence on performance in dye-sensitized solar cells. The pyridine-anchor zinc phthalocyanine sensitizer PcS23 shows 79 % incident-photon to current-conversion efficiency (IPCE) and 6.1 % energy conversion efficiency, which are comparable with similar phthalocyanine dyes having a carboxylic acid anchoring group. Based on DFT calculations, the high IPCE is attributed with the mixture of an excited-state molecular orbital of the sensitizer and the orbitals of TiO2 . Between pyridine and carboxylic acid anchor dyes, opposite trends are observed in the linker-length dependence of the IPCE. The red-absorbing PcS23 is applied for co-sensitization with a carboxyl-anchor organic dye D131 that has a complementary spectral response. The site-selective adsorption of PcS23 and D131 on the TiO2 surface results in a panchromatic photocurrent response for the whole visible-light region of sun light. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photo-antimicrobial efficacy of zinc complexes of porphyrin and phthalocyanine activated by inexpensive consumer LED lamp.

PubMed

George, Lijo; Hiltunen, Arto; Santala, Ville; Efimov, Alexander

2018-06-01

The properties and antimicrobial efficacies of zinc complexes of tetrakis(N-methylpyridinium-4-yl) tetraiodide porphyrin and tetrakis(N-methylpyridinium-4-yl) tetraiodide phthalocyanine impregnated to paper were evaluated. Photo-inactivation of microbes using inexpensive consumer light-emitting diode lamp was assessed on surface of dyed papers. Antimicrobial experiments of phthalocyanine-dyed paper by live cell assessment through colony forming units counting demonstrated 3.72 and 4.01 log reduction against Escherichia coli (E. coli) and Acinetobacter baylyi (A. baylyi) respectively after 1 h of illumination with 35 mW/cm 2 light. The porphyrin-dyed paper exhibited 1.66 and 2.01 log reduction in colony forming units against E. coli and A. baylyi respectively after 1 h exposure with 4 mW/cm 2 light. Both dyed papers were photo-stable after 64 h of continuous exposure with 42 mW/cm 2 light, while phthalocyanine-dyed paper exhibited superior leaching stability in phosphate-buffered saline. Copyright © 2018 Elsevier Inc. All rights reserved.

Iodinated Al(III)-based phthalocyanines are promising sensitizers for dye-sensitized solar cells; a theoretical comparison between Zn(II), Mg(II), and Al(III)-based phthalocyanine sensitizers.

PubMed

Yang, Li-Na; Sun, Zhu-Zhu; Chen, Shi-Lu; Li, Ze-Sheng

2014-02-24

To design efficient dyes for dye-sensitized solar cells (DSSCs), using a Zn-coordinated phthalocyanine (TT7) as the prototype, a series of phthalocyanine dyes (Pcs) with different metal ions and peripheral/axial groups have been investigated by means of density functional theory (DFT) and time-dependent DFT (TDDFT) methods. Computational results show that the iodinated Al-based dye with a peripheral amino group (Al-I-NH2-Pc) exhibits the largest redshift in the maximum absorbance (λ(max)). In addition, Al-based dyes have appropriate energy-level arrangements of frontier orbitals to keep excellent balance between electron injection and regeneration of oxidized dyes. Further, it has been found that the intermolecular π-staking interaction in Al-I-Pc molecules is weaker than the other metal-based Pcs, which may effectively reduce dye aggregation on the semi-conductor surface. All these results suggest iodinated Al-based Pcs (Al-I-Pcs) to be potentially promising sensitizers in DSSCs. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen-Bonded Organic Semiconductor Micro- And Nanocrystals: From Colloidal Syntheses to (Opto-)Electronic Devices

PubMed Central

2014-01-01

Organic pigments such as indigos, quinacridones, and phthalocyanines are widely produced industrially as colorants for everyday products as various as cosmetics and printing inks. Herein we introduce a general procedure to transform commercially available insoluble microcrystalline pigment powders into colloidal solutions of variously sized and shaped semiconductor micro- and nanocrystals. The synthesis is based on the transformation of the pigments into soluble dyes by introducing transient protecting groups on the secondary amine moieties, followed by controlled deprotection in solution. Three deprotection methods are demonstrated: thermal cleavage, acid-catalyzed deprotection, and amine-induced deprotection. During these processes, ligands are introduced to afford colloidal stability and to provide dedicated surface functionality and for size and shape control. The resulting micro- and nanocrystals exhibit a wide range of optical absorption and photoluminescence over spectral regions from the visible to the near-infrared. Due to excellent colloidal solubility offered by the ligands, the achieved organic nanocrystals are suitable for solution processing of (opto)electronic devices. As examples, phthalocyanine nanowire transistors as well as quinacridone nanocrystal photodetectors, with photoresponsivity values by far outperforming those of vacuum deposited reference samples, are demonstrated. The high responsivity is enabled by photoinduced charge transfer between the nanocrystals and the directly attached electron-accepting vitamin B2 ligands. The semiconducting nanocrystals described here offer a cheap, nontoxic, and environmentally friendly alternative to inorganic nanocrystals as well as a new paradigm for obtaining organic semiconductor materials from commercial colorants. PMID:25253644

The effect of the triblock properties on the morphologies and photophysical properties of nanoparticle loaded with carboxylic dendrimer phthalocyanine

NASA Astrophysics Data System (ADS)

Lv, Huafei; Chen, Zhe; Yu, Xinxin; Pan, Sujuan; Zhang, Tiantian; Xie, Shusen; Yang, Hongqin; Peng, Yiru

2016-09-01

Photodynamic therapy (PDT) is an emerging alternative treatment for various cancers and age-related macular degeneration. Phthalocyanines (Pcs) and their substituted derivatives are under intensive investigation as the second generation photosensitizers. A big challenge for the application of Pcs is poor solubility and limited accumulation in the tumor tissues, which severely reduced its PDT efficacy. Nano-delivery systems such as polymeric micelles are promising tools for increasing the solubility and improving delivery efficiency of Pcs for PDT application. In this paper, nanoparticles of amphiphilic triblock copolymer poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) were developed to encapsulate 1-2 generation carboxylic poly (benzyl aryl ether) dendrimer. The morphologies and photophysical properties of polymeric nanoparticles loaded with 1-2 generation dendritic phthalocyanines (G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m) were studied by AFM, UV/Vis and fluorescent spectroscopic method. The morphologies of self-assembled PLL-PEG-PLL aggregates exhibited concentration dependence. Its morphologies changed from cocoon-like to spheral. The diameters of G1-ZnPc(COOH)8/m and G2-ZnPc(COOH)16/m were in the range of 33-147 nm, increasing with the increase of the concentration of PLL-PEG-PLL. The morphologies of G2-ZnPc(COOH)16/m also changed from cocoon-like to sphere with the increase of the concentration of PLL-PEG-PLL. It was found that, the no obviously Q change was observed between the free phthalocyanines and nanoparticles. The fluorescence intensity of polymer nanoparticles were higher enhanced compared with free dendritic phthalocyanines. The dendrimer phthalocyanine loaded with poly(L-lysine)-b-poly (ethylene glycol)-b-poly(L-lysine) presented suitable physical stability, improved photophysical properties suggesting it may be considered as a promising formulation for PDT.

Tetrabutylammonium Salts of Aluminum(III) and Gallium(III) Phthalocyanine Radical Anions Bonded with Fluoren-9-olato- Anions and Indium(III) Phthalocyanine Bromide Radical Anions.

PubMed

Konarev, Dmitri V; Khasanov, Salavat S; Ishikawa, Manabu; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Saito, Gunzi; Lyubovskaya, Rimma N

2017-04-18

Reduction of aluminum(III), gallium(III), and indium(III) phthalocyanine chlorides by sodium fluorenone ketyl in the presence of tetrabutylammonium cations yielded crystalline salts of the type (Bu 4 N + ) 2 [M III (HFl-O - )(Pc .3- )] .- (Br - )⋅1.5 C 6 H 4 Cl 2 [M=Al (1), Ga (2); HFl-O - =fluoren-9-olato - anion; Pc=phthalocyanine] and (Bu 4 N + ) [In III Br(Pc .3- )] .- ⋅0.875 C 6 H 4 Cl 2 ⋅0.125 C 6 H 14 (3). The salts were found to contain Pc .3- radical anions with negatively charged phthalocyanine macrocycles, as evidenced by the presence of intense bands of Pc .3- in the near-IR region and a noticeable blueshift in both the Q and Soret bands of phthalocyanine. The metal(III) atoms coordinate HFl-O - anions in 1 and 2 with short Al-O and Ga-O bond lengths of 1.749(2) and 1.836(6) Å, respectively. The C-O bonds [1.402(3) and 1.391(11) Å in 1 and 2, respectively] in the HFl-O - anions are longer than the same bond in the fluorenone ketyl (1.27-1.31 Å). Salts 1-3 show effective magnetic moments of 1.72, 1.66, and 1.79 μ B at 300 K, respectively, owing to the presence of unpaired S=1/2 spins on Pc .3- . These spins are coupled antiferromagnetically with Weiss temperatures of -22, -14, and -30 K for 1-3, respectively. Coupling can occur in the corrugated two-dimensional phthalocyanine layers of 1 and 2 with an exchange interaction of J/k B =-0.9 and -1.1 K, respectively, and in the π-stacking {[In III Br(Pc .3- )] .- } 2 dimers of 3 with an exchange interaction of J/k B =-10.8 K. The salts show intense electron paramagnetic resonance (EPR) signals attributed to Pc .3- . It was found that increasing the size of the central metal atom strongly broadened these EPR signals. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

LASERS IN MEDICINE: Two-photon excitation of aluminium phthalocyanines

NASA Astrophysics Data System (ADS)

Meshalkin, Yu P.; Alfimov, E. E.; Vasil'ev, N. E.; Denisov, A. N.; Makukha, V. K.; Ogirenko, A. P.

1999-12-01

A demonstration is given of the feasibility of two-photon excitation of aluminium phthalocyanine and of the pharmaceutical preparation 'Fotosens', used in photodynamic therapy. The excitation source was an Nd:YAG laser emitting at the 1064 nm wavelength. The spectra of the two-photon-excited luminescence were obtained and the two-photon absorption cross sections were determined.

Strongly enhanced Raman scattering of Cu-phthalocyanine sandwiched between graphene and Au(111).

PubMed

Lin, Wan-Ing; Gholami, Mohammad Fardin; Beyer, Paul; Severin, Nikolai; Shao, Feng; Zenobi, Renato; Rabe, Jürgen P

2017-01-05

Graphene and flat gold have both been argued to enhance Raman scattering of molecular adsorbates through a chemical mechanism. Here we show that these two effects can add to each other. For Cu-phthalocyanine in between graphene and Au(111) on mica a Raman enhancement up to 68-fold has been observed.

Improved photocatalytic degradation of Orange G using hybrid nanofibers

NASA Astrophysics Data System (ADS)

Ledwaba, Mpho; Masilela, Nkosiphile; Nyokong, Tebello; Antunes, Edith

2017-05-01

Functionalised electrospun polyamide-6 (PA-6) nanofibres incorporating gadolinium oxide nanoparticles conjugated to zinc tetracarboxyphenoxy phthalocyanine (ZnTCPPc) as the sensitizer were prepared for the photocatalytic degradation of Orange G. Fibres incorporating the phthalocyanine alone or a mixture of the nanoparticles and phthalocyanine were also generated. The singlet oxygen-generating ability of the sensitizer was shown to be maintained within the fibre mat, with the singlet oxygen quantum yields increasing upon incorporation of the magnetic nanoparticles. Consequently, the rate of the photodegradation of Orange G was observed to increase with an increase in singlet oxygen quantum yield. A reduction in the half-lives for the functionalised nanofibres was recorded in the presence of the magnetic nanoparticles, indicating an improvement in the efficiency of the degradation process.

Facile fabrication of dual emissive nanospheres via the self-assembling of CdSe@CdS and zinc phthalocyanine and their application for silver ion detection

NASA Astrophysics Data System (ADS)

Liu, Shuning; Liu, Chenchen; Luan, Xinying; Yao, Rui; Feng, Yakai

2017-09-01

The far-red/near infrared photoluminescence of zinc phthalocyanines would be strongly quenched once they are aggregated, which will obviously hinder their wide applications in environmental, energy related and biomedical fields. Herein, the ultra-small sized semiconductor quantum dots with core-shell structures (CdSe@CdS) have been firstly synthesized and then assembled with a dendritic zinc phthalocyanine (ZnPc) in the H2O/DMF mixed solvent to obtain monodispersed nanospheres. Finally, it was found that the resultant ethanolic colloids can be employed as a sensitive and specific fluorescent nanoprobe for silver ions discrimination with a limit of detection (LOD) approaching to 10-8 mol/L.

Evaluation of the Intramolecular Charge-Transfer Properties in Solvatochromic and Electrochromic Zinc Octa(carbazolyl)phthalocyanines.

PubMed

Majeed, Shereen A; Ghazal, Basma; Nevonen, Dustin E; Goff, Philip C; Blank, David A; Nemykin, Victor N; Makhseed, Saad

2017-10-02

2,3,9,10,16,17,23·24-Octakis-(9H-carbazol-9-yl) phthalocyaninato zinc(II) (3) and 2,3,9,10,16,17,23·24-octakis-(3,6-di-tert-butyl-9H-carbazole) phthalocyaninato zinc(II) (4) complexes were prepared and characterized by NMR and UV-vis spectroscopies, magnetic circular dichroism (MCD), matrix-assisted laser desorption ionization mass spectrometry, and X-ray crystallography. UV-vis and MCD data are indicative of the interligand charge-transfer nature of the broad band observed in 450-500 nm range for 3 and 4. The redox properties of 3 and 4 were probed by electrochemical and spectro-electrochemical methods, which are suggestive of phthalocyanine-centered first oxidation and reduction processes. Photophysics of 3 and 4 were investigated by steady-state fluorescence and time-resolved transient absorption spectroscopy demonstrating the influence of the carbazole substituents on deactivation from the first excited state in 3 and 4. Protonation of the meso-nitrogen atoms in 3 results in much faster deactivation kinetics from the first excited state. Spectroscopic data were correlated with density functional theory (DFT) and time-dependent DFT calculations on 3 and 4.

Nanostructured copper phthalocyanine-sensitized multiwall carbon nanotube films.

PubMed

Hatton, Ross A; Blanchard, Nicholas P; Stolojan, Vlad; Miller, Anthony J; Silva, S Ravi P

2007-05-22

We report a detailed study of the interaction between surface-oxidized multiwall carbon nanotubes (o-MWCNTs) and the molecular semiconductor tetrasulfonate copper phthalocyanine (TS-CuPc). Concentrated dispersions of o-MWCNT in aqueous solutions of TS-CuPc are stable toward nanotube flocculation and exhibit spontaneous nanostructuring upon rapid drying. In addition to hydrogen-bonding interactions, the compatibility between the two components is shown to result from a ground-state charge-transfer interaction with partial charge transfer from o-MWCNT to TS-CuPc molecules orientated such that the plane of the macrocycle is parallel to the nanotube surface. The electronegativity of TS-CuPc as compared to unsubsubtituted copper phthalocyanine is shown to result from the electron-withdrawing character of the sulfonate substituents, which increase the molecular ionization potential and promote cofacial molecular aggregation upon drying. Upon spin casting to form uniform thin films, the experimental evidence is consistent with an o-MWCNT scaffold decorated with phthalocyanine molecules self-assembled into extended aggregates reminiscent of 1-D linearly stacked phthalocyanine polymers. Remarkably, this self-organization occurs in a fraction of a second during the spin-coating process. To demonstrate the potential utility of this hybrid material, it is successfully incorporated into a model organic photovoltaic cell at the interface between a poly(3-hexylthiophene):[6,6]-phenyl-C61 butyric acid methyl ester bulk heterojunction layer and an indium-tin oxide-coated glass electrode to increase the light-harvesting capability of the device and facilitate hole extraction. The resulting enhancement in power conversion efficiency is rationalized in terms of the electronic, optical, and morphological properties of the nanostructured thin film.

Face-on stacking and enhanced out-of-plane hole mobility in graphene-templated copper phthalocyanine.

PubMed

Mativetsky, Jeffrey M; Wang, He; Lee, Stephanie S; Whittaker-Brooks, Luisa; Loo, Yueh-Lin

2014-05-25

Efficient out-of-plane charge transport is required in vertical device architectures, such as organic solar cells and organic light emitting diodes. Here, we show that graphene, transferred onto different technologically-relevant substrates, can be used to induce face-on molecular stacking and improve out-of-plane hole transport in copper phthalocyanine thin films.

Electronic absorption band broadening and surface roughening of phthalocyanine double layers by saturated solvent vapor treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jinhyun; Yim, Sanggyu, E-mail: sgyim@kookmin.ac.kr

2012-10-15

Variations in the electronic absorption (EA) and surface morphology of three types of phthalocyanine (Pc) thin film systems, i.e. copper phthalocyanine (CuPc) single layer, zinc phthalocyanine (ZnPc) single layer, and ZnPc on CuPc (CuPc/ZnPc) double layer film, treated with saturated acetone vapor were investigated. For the treated CuPc single layer film, the surface roughness slightly increased and bundles of nanorods were formed, while the EA varied little. In contrast, for the ZnPc single layer film, the relatively high solubility of ZnPc led to a considerable shift in the absorption bands as well as a large increase in the surface roughnessmore » and formation of long and wide nano-beams, indicating a part of the ZnPc molecules dissolved in acetone, which altered their molecular stacking. For the CuPc/ZnPc film, the saturated acetone vapor treatment resulted in morphological changes in mainly the upper ZnPc layer due to the significantly low solubility of the underlying CuPc layer. The treatment also broadened the EA band, which involved a combination of unchanged CuPc and changed ZnPc absorption.« less

pH-Responsive Dimeric Zinc(II) Phthalocyanine in Mesoporous Silica Nanoparticles as an Activatable Nanophotosensitizing System for Photodynamic Therapy.

PubMed

Wong, Roy C H; Chow, Sun Y S; Zhao, Shirui; Fong, Wing-Ping; Ng, Dennis K P; Lo, Pui-Chi

2017-07-19

An acid-cleavable acetal-linked zinc(II) phthalocyanine dimer with an azido terminal group (cPc) was prepared and conjugated to alkyne-modified mesoporous silica nanoparticles via copper(I)-catalyzed alkyne-azide cycloaddition reaction. For comparison, an amine-linked analogue (nPc) was also prepared as a non-acid-cleavable counterpart. These dimeric phthalocyanines were significantly self-quenched due to the close proximity of the phthalocyanine units inside the mesopores, resulting in much weaker fluorescence emission and singlet oxygen generation, both in N,N-dimethylformamide and in phosphate-buffered saline (PBS), compared with the free molecular counterparts. Under acidic conditions in PBS, the cPc-encapsulated nanosystem was activated in terms of fluorescence emission and singlet oxygen production. After internalization into human colon adenocarcinoma HT29 cells, it exhibited much higher intracellular fluorescence and photocytotoxicity compared to the nanosystem entrapped with nPc. The activation of this nanosystem was also demonstrated in tumor-bearing nude mice. The intratumoral fluorescence intensity increased gradually over 24 h, while for the nPc counterpart the fluorescence remained very weak. The results suggest that this nanosystem serves as a promising activatable nanophotosensitizing agent for photodynamic therapy.

An Electrochemical Quartz Crystal Microbalance Multisensor System Based on Phthalocyanine Nanostructured Films: Discrimination of Musts

PubMed Central

Garcia-Hernandez, Celia; Medina-Plaza, Cristina; Garcia-Cabezon, Cristina; Martin-Pedrosa, Fernando; del Valle, Isabel; de Saja, Jose Antonio; Rodríguez-Méndez, Maria Luz

2015-01-01

An array of electrochemical quartz crystal electrodes (EQCM) modified with nanostructured films based on phthalocyanines was developed and used to discriminate musts prepared from different varieties of grapes. Nanostructured films of iron, nickel and copper phthalocyanines were deposited on Pt/quartz crystals through the Layer by Layer technique by alternating layers of the corresponding phthalocyanine and poly-allylamine hydrochloride. Simultaneous electrochemical and mass measurements were used to study the mass changes accompanying the oxidation of electroactive species present in must samples obtained from six Spanish varieties of grapes (Juan García, Prieto Picudo, Mencía Regadío, Cabernet Sauvignon, Garnacha and Tempranillo). The mass and voltammetric outputs were processed using three-way models. Parallel Factor Analysis (PARAFAC) was successfully used to discriminate the must samples according to their variety. Multi-way partial least squares (N-PLS) evidenced the correlations existing between the voltammetric data and the polyphenolic content measured by chemical methods. Similarly, N-PLS showed a correlation between mass outputs and parameters related to the sugar content. These results demonstrated that electronic tongues based on arrays of EQCM sensors can offer advantages over arrays of mass or voltammetric sensors used separately. PMID:26610494

Supramolecular organization of pi-conjugated molecules monitored by single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Alvarez, Laurent; Almadori, Yann; Belhboub, Anouar; Le Parc, Rozenn; Aznar, Raymond; Dieudonné-George, Philippe; Rahmani, Abdelali; Hermet, Patrick; Fossard, Frédéric; Loiseau, Annick; Jousselme, Bruno; Campidelli, Stéphane; Saito, Takeshi; Wang, Guillaume; Bantignies, Jean-Louis

2016-03-01

Photoactive pi-conjugated molecules (quaterthiophene and phthalocyanine) are either encapsulated into the hollow core of single-walled carbon nanotubes or noncovalently stacked at their outer surface in order to elaborate hybrid nanosystems with new physical properties, providing practical routes to fit different requirements for potential applications. We are interested in the relationship between the structure and the optoelectronic properties. The structural properties are investigated mainly by x-ray diffraction and/or transmission electron microscopy and Raman spectroscopy. We show that the supramolecular organizations of confined quaterthiophenes depend on the nanocontainer size, whereas phthalocyanine encapsulation leads to the formation of a one-dimensional phase for which the angle between the molecule ring and the nanotube axis is close to 32 deg. Confined phthalocyanine molecules display Raman spectra hardly altered with respect to the bulk phase, suggesting a rather weak interaction with the tubes. In contrast, the vibrational properties of the molecules stacked at the outer surface of tubes display important modifications. We assume a significant curvature of the phthalocyanine induced by the interaction with the tube walls and a change of the central atom position within the molecular ring, in good agreement with our density functional theory calculations.

Distribution of phthalocyanines and Raman reporters in human cancerous and noncancerous breast tissue as studied by Raman imaging.

PubMed

Brozek-Pluska, Beata; Jarota, Arkadiusz; Jablonska-Gajewicz, Joanna; Kordek, Radzislaw; Czajkowski, Wojciech; Abramczyk, Halina

2012-08-01

There is a considerable interest in the developing new diagnostic techniques allowing noninvasive tracking of the progress of therapies used to treat a cancer. Raman imaging of distribution of phthalocyanine photosensitizers may open new possibilities of Photodynamic Therapy (PDT) to treat a wide range of neoplastic lesions with improved effectiveness of treatment through precise identification of malignant areas. We have employed Raman imaging and Raman spectroscopy to analyze human breast cancer tissue that interacts with photosensitizers used in the photodynamic therapy of cancer. PCA (Principal Component Analysis) has been employed to analyze various areas of the noncancerous and cancerous breast tissues. The results show that the emission spectra combined with the Raman images are very sensitive indicators to specify the aggregation state and the distribution of phthalocyanines in the cancerous and noncancerous breast tissues. Our results provide experimental evidence on the role of aggregation of phthalocyanines as a factor of particular significance in differentiation of the normal and tumourous (cancerous or benign pathology) breast tissues. We conclude that the Raman imaging reported here has a potential to be a novel and effective photodynamic therapeutic method with improved selectivity for the treatment of breast cancer.

Effect of axial ligation and delivery system on the tumour-localising and -photosensitising properties of Ge(IV)-octabutoxy-phthalocyanines.

PubMed Central

Soncin, M.; Polo, L.; Reddi, E.; Jori, G.; Kenney, M. E.; Cheng, G.; Rodgers, M. A.

1995-01-01

Four Ge(IV)-octabutoxy-phthalocyanines (GePcs) bearing two alkyl-type axial ligands were assayed for their pharmacokinetic properties and phototherapeutic efficiency in Balb/c mice bearing an intramuscularly transplanted MS-2 fibrosarcoma. The GePcs were i.v. injected at a dose of 0.35 mumol kg-1 body weight after incorporation into either Cremophor emulsions or small unilamellar liposomes of dipalmitoyl-phosphatidylcholine (DPPC). Both the nature of the delivery system and the chemical structure of the phthalocyanine were found to affect the behaviour of the GePcs in vivo. Thus, Cremophor-administered GePcs invariably yielded a more prolonged serum retention and a larger association with low-density lipoproteins (LDLs) as compared with the corresponding liposome-delivered phthalocyanines. This led to a greater efficiency and selectivity of tumour targeting. These effects were more pronounced for those GePcs having relatively long alkyl chains (hexyl to decyl) in the axial ligands. Maximal tumour accumulation (0.67 nmol per g of tissue) was found for Ge-Pc(hexyl)2 at 24 h after injection. Consistently, the Ge-Pc(hexyl)2, administered via Cremophor, showed the highest phototherapeutic activity towards MS-2 fibrosarcoma. PMID:7710936

FAST TRACK COMMUNICATION Tuning the spin state of iron phthalocyanine by ligand adsorption

NASA Astrophysics Data System (ADS)

Isvoranu, C.; Wang, B.; Schulte, K.; Ataman, E.; Knudsen, J.; Andersen, J. N.; Bocquet, M. L.; Schnadt, J.

2010-12-01

The future use of single-molecule magnets in applications will require the ability to control and manipulate the spin state and magnetization of the magnets by external means. There are different approaches to this control, one being the modification of the magnets by adsorption of small ligand molecules. In this paper we use iron phthalocyanine supported by an Au(111) surface as a model compound and demonstrate, using x-ray photoelectron spectroscopy and density functional theory, that the spin state of the molecule can be tuned to different values (S ~ 0, \\case {1}{2} , 1) by adsorption of ammonia, pyridine, carbon monoxide or nitric oxide on the iron ion. The interaction also leads to electronic decoupling of the iron phthalocyanine from the Au(111) support.

Adlayer structure of octa-alkoxy-substituted copper(II) phthalocyanine on Au(111) by electrochemical scanning tunneling microscopy.

PubMed

Wang, Li; Ou-Yang, Liangyue; Yau, Shueh-Lin

2008-01-01

Electrochemical scanning tunneling microscopy (ECSTM) has been used to examine the adlayer of octa-alkoxy-substituted copper(II) phthalocyanines (CuPc(OC(8)H(17))(8)) on Au(111) in 0.1 M HClO(4), where the molecular adlayer was prepared by spontaneous adsorption from a benzene solution containing this molecule. Topography STM scans revealed long-range ordered, interweaved arrays of CuPc(OC(8)H(17))(8) with coexistent rectangular and hexagonal symmetries. High-quality STM molecular resolution yielded the internal molecular structure and the orientation of CuPc(OC(8)H(17))(8) admolecules. These STM results could shed insight into the method of generating ordered molecular assemblies of phthalocyanine molecules with long-chained substitutes on metal surface. 2007 Wiley-Liss, Inc

The production of copper phthalocyanine and/or its derivatives

NASA Technical Reports Server (NTRS)

Segawa, T.; Matsuzaki, K.; Sawada, H.; Ninomiya, R.; Suyama, M.

1984-01-01

This document discusses the production of copper phthalocyanine and/or its derivatives, which are useful for dye pigments. The method described uses urea, a copper compound and/or a catalyst which have been suspended in an inert reaction medium. The copper compound, catalyst and urea fused and the reaction is performed by using the obtained fusion. The advantages of the invention are listed.

Corrosion Inhibitors for Metals in Naval Environments

DTIC Science & Technology

1988-06-15

chlorides (PCCOCl) were treated with an amino acid containing a long aliphatic chain (either li-aminoundecanoic acid or 6- aminocaproic acid ) to give the long...phthalocyanines as corrosion inhibiting coatings - poyeriz by decarboxylation of chloroiron (Il1) tetracarboxcyphthalocyanine and reacting the acid chloride...by converting the tetracarboxy- phthalocyanines to the corresponding acid chloride and reacting the acid chloride with amino acids containing 6 or 12

Cation or Solvent-Induced Supermolecular Phthalocyanine Formation: Crown Ether Substituted Phthalocyanines.

DTIC Science & Technology

1987-06-01

38.) of slightly bluish green powder (Anal, see Table I). tH NMR(CDCl 3 ) 8.02(8H,s), 4.7-3.6(64H,m), - 3.41(2H,s). ZnCRPc was obtained by reaction of...J.P.; Bencosme, S.; Evitt, E., Sessler, J. Chem. Phys. 1984, 86, 161. Mialoco, C.; Giannotti, A., Maillard , P.; Momeuteau, M. Chem. Phys. Lett. 1984

Location of Varying Hydrophobicity Zinc(II) Phthalocyanine-Type Photosensitizers in Methoxy Poly(ethylene oxide) and Poly(l-lactide) Block Copolymer Micelles Using 1H NMR and XPS Techniques.

PubMed

Lamch, Łukasz; Tylus, Włodzimierz; Jewgiński, Michał; Latajka, Rafał; Wilk, Kazimiera A

2016-12-15

Hydrophobic zinc(II) phthalocyanine-type derivatives, solubilized in polymeric micelles (PMs), provide a befitting group of so-called nanophotosensitizers, suitable for a variety of photodynamic therapy (PDT) protocols. The factors that influence the success of such products in PDT are the location of the active cargo in the PMs and the nanocarrier-enhanced ability to safely interact with biological systems and fulfill their therapeutic functions. Therefore, the aim of this work was to determine the solubilization loci of three phthalocyanines of varying hydrophobicity, i.e., zinc(II) phthalocyanine (ZnPc), along with its tetrasulfonic acid (ZnPc-sulfo 4 ) and perfluorinated (ZnPcF 16 ) derivatives, loaded in polymeric micelles of methoxy poly(ethylene oxide)-b-poly(l-lactide) (mPEG-b-PLLA), by means of 1 H nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) combined with ion sputtering. Furthermore, the microenvironment influence upon the chemical and physical status of the solubilized cargo in PMs, expressed by photobleaching and reactive oxygen species (ROS) generation comparing to the same properties of native cargoes in solution, was also evaluated and discussed in regards to the probing location data. The studied phthalocyanine-loaded PMs exhibited good physical stability, high drug-loading efficiency, and a size of less than ca. 150 nm with low polydispersity indices. The formation of polymeric micelles and the solubilization locus were investigated by 1 H NMR and XPS. ZnPc localized within the PM core, whereas both ZnPcF 16 and ZnPc-sulfo 4 - in the corona of PMs. We proved that the cargo locus is crucial for the photochemical properties of the studied phthalocyanines; the increase in photostability and ability to generate ROS in micellar solution compared to free photosensitizer was most significant for the photosensitizer in the PM core. Our results indicate the role of the cargo location in the PM microenvironment and demonstrate that such attempts are fundamental for improving the properties of photosensitizers and their assumed efficiency as nanophotosensitizers in PDT.

Molecular Mechanism of Uptake of Cationic Photoantimicrobial Phthalocyanine across Bacterial Membranes Revealed by Molecular Dynamics Simulations.

PubMed

Orekhov, Philipp S; Kholina, Ekaterina G; Bozdaganyan, Marine E; Nesterenko, Alexey M; Kovalenko, Ilya B; Strakhovskaya, Marina G

2018-04-12

Phthalocyanines are aromatic macrocyclic compounds, which are structurally related to porphyrins. In clinical practice, phthalocyanines are used in fluorescence imaging and photodynamic therapy of cancer and noncancer lesions. Certain forms of the substituted polycationic metallophthalocyanines have been previously shown to be active in photodynamic inactivation of both Gram-negative and Gram-positive bacteria; one of them is zinc octakis(cholinyl)phthalocyanine (ZnPcChol 8+ ). However, the molecular details of how these compounds translocate across bacterial membranes still remain unclear. In the present work, we have developed a coarse-grained (CG) molecular model of ZnPcChol 8+ within the framework of the popular MARTINI CG force field. The obtained model was used to probe the solvation behavior of phthalocyanine molecules, which agreed with experimental results. Subsequently, it was used to investigate the molecular details of interactions between phthalocyanines and membranes of various compositions. The results demonstrate that ZnPcChol 8+ has high affinity to both the inner and the outer model membranes of Gram-negative bacteria, although this species does not show noticeable affinity to the 1-palmitoyl-2-oleoyl- sn-glycero-3-phosphatidylcholine membrane. Furthermore, we found out that the process of ZnPcChol 8+ penetration toward the center of the outer bacterial membrane is energetically favorable and leads to its overall disturbance and formation of the aqueous pore. Such intramembrane localization of ZnPcChol 8+ suggests their twofold cytotoxic effect on bacterial cells: (1) via induction of lipid peroxidation by enhanced production of reactive oxygen species (i.e., photodynamic toxicity); (2) via rendering the bacterial membrane more permeable for additional Pc molecules as well as other compounds. We also found that the kinetics of penetration depends on the presence of phospholipid defects in the lipopolysaccharide leaflet of the outer membrane and the type of counterions, which stabilize it. Thus, the results of our simulations provide a detailed molecular view of ZnPcChol 8+ "self-promoted uptake", the pathway previously proposed for some small molecules crossing the outer bacterial membrane.

Phototoxic effect of aluminium-chlorine and aluminium-hydroxide phthalocyanines on Leishmania (l.) amazonensis.

PubMed

Nesi-Reis, V; Navasconi, T R; Lera-Nosone, D S S L; Oliveira, E L; Barbosa, P M; Caetano, W; Silveira, T G V; Aristides, S M A; Hioka, N; Lonardoni, M V C

2018-03-01

This study investigated the activity of photosensitive phthalocyanines on promastigotes and amastigotes of Leishmania (L.) amazonensis. Aluminum phthalocyanine chloride (AlPcCl), Aluminum phthalocyanine hydroxide (AlPcOH) and zinc phthalocyanine (PcZn) were tested in the presence (matte red LED, potency of 2.5-2.3 μW for 30 min) and absence of light against L. amazonensis promastigotes and the parasite viability was evaluated after 24, 48 and 72 h. The amastigote forms were treated with AlPcCl and AlPcOH, following the same lighting protocols described for the promastigote forms, being evaluated after 24 h. Cytotoxicity to human erythrocytes and peritoneal macrophages was also evaluated. The results showed that AlPcCl and AlPcOH in the presence of light have antileishmania activity, with leishmanistatic effects on promastigotes and amastigotes of L. amazonensis, without causing cytotoxicity to peritoneal macrophages and erythrocytes. The concentrations that inhibited 50% of the promastigote forms after 24 h of light exposure were 0.21 ± 0.08 μM for AlPcCl and 0.23 ± 0.06 μM for AlPcOH. In 48 h and 72 h after the treatment, the IC 50 of AlPcCl was 0.13 ± 0.02 and 0.12 ± 0.03 μM and for AlPcOH was 0.14 ± 0.01 μM and 0.11 ± 0.01 μM, respectively. PcZn showed no activity on promastigotes of L. amazonensis. This study showed a substantial photodynamic activity of the phthalocyanines AlPcCl and AlPcOH against intracellular amastigotes forms of L. amazonensis after irradiation, presenting IC 50 values of 0.62 ± 0.06 μM and 0.92 ± 0.12 μM, respectively. These results support the possibility of using photodynamic therapy for the treatment of cutaneous leishmaniasis. Copyright © 2017 Elsevier B.V. All rights reserved.

Matrix effects on copper(II)phthalocyanine complexes. A combined continuous wave and pulse EPR and DFT study.

PubMed

Finazzo, Cinzia; Calle, Carlos; Stoll, Stefan; Van Doorslaer, Sabine; Schweiger, Arthur

2006-04-28

The effect of the electron withdrawing or donating character of groups located at the periphery of the phthalocyanine ligand, as well as the influence of polar and nonpolar solvents are of importance for the redox chemistry of metal phthalocyanines. Continuous wave and pulse electron paramagnetic resonance and pulse electron nuclear double resonance spectroscopy at X- and Q-band are applied to investigate the electronic structure of the complexes Cu(II)phthalocyanine (CuPc), copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPc(t)), and copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine (CuPc(F)) in various matrices. Isotope substitutions are used to determine the g values, the copper hyperfine couplings and the hyperfine interactions with the 14N, 1H and 19F nuclei of the macrocycle and the surrounding matrix molecules. Simulations and interpretations of the spectra are shown and discussed, and a qualitative analysis of the data using previous theoretical models is given. Density functional computations facilitate the interpretation of the EPR parameters. The experimental g, copper and nitrogen hyperfine and nuclear quadrupole values are found to be sensitive to changes of the solvent and the structure of the macrocycle. To elucidate the electronic, structural and bonding properties the changes in the g principal values are related to data from UV/Vis spectroscopy and to density functional theory (DFT) computations. The analysis of the EPR data indicates that the in-plane metal-ligand sigma bonding is more covalent for CuPc(t) in toluene than in sulfuric acid. Furthermore, the out-of-plane pi bonding is found to be less covalent in the case of a polar sulfuric acid environment than with nonpolar toluene or H2Pc environment, whereby the covalency of this bonding is increased upon addition of tert-butyl groups. No contribution from in-plane pi bonding is found.

Synthesis and strong optical limiting response of graphite oxide covalently functionalized with gallium phthalocyanine

NASA Astrophysics Data System (ADS)

Li, Yong-Xi; Zhu, Jinhui; Chen, Yu; Zhang, Jinjuan; Wang, Jun; Zhang, Bin; He, Ying; Blau, Werner J.

2011-05-01

A soluble graphite oxide (GO) axially substituted gallium phthalocyanine (PcGa) hybrid material (GO-PcGa) was for the first time synthesized by the reaction of tBu4PcGaCl with GO in anhydrous DMSO at 110 °C in the presence of K2CO3. The formation of a Ga-O bond between PcGa and GO has been confirmed by x-ray photoelectron spectroscopy. In contrast to GO, the D and G bands of GO-PcGa in the Raman spectrum are shifted to the lower wavenumbers by Δν = 11 and 18 cm - 1, respectively. At the same level of concentration of 0.1 g l - 1, GO-PcGa exhibit much larger nonlinear optical extinction coefficients and strong optical limiting performance than GO, tBu4PcGaCl and C60 at both 532 and 1064 nm, implying a remarkable accumulation effect as a result of the covalent link between GO and PcGa. GO-PcGa possesses three main mechanisms for the nonlinear optical response—nonlinear light scattering, two-photon absorption and reverse saturable absorption for the 532 nm pulses and nonlinear light scattering for the 1064 nm pulses. tBu4PcGaCl does not make any significant contribution to the optical limiting at 1064 nm, while GO-PcGa has a much greater optical limiting response than GO at this wavelength, this suggesting that the PcGa moiety could certainly play an unknown but important role in the GO-PcGa material system.

Importance of semicore states in GW calculations for simulating accurately the photoemission spectra of metal phthalocyanine molecules.

PubMed

Umari, P; Fabris, S

2012-05-07

The quasi-particle energy levels of the Zn-Phthalocyanine (ZnPc) molecule calculated with the GW approximation are shown to depend sensitively on the explicit description of the metal-center semicore states. We find that the calculated GW energy levels are in good agreement with the measured experimental photoemission spectra only when explicitly including the Zn 3s and 3p semicore states in the valence. The main origin of this effect is traced back to the exchange term in the self-energy GW approximation. Based on this finding, we propose a simplified approach for correcting GW calculations of metal phthalocyanine molecules that avoids the time-consuming explicit treatment of the metal semicore states. Our method allows for speeding up the calculations without compromising the accuracy of the computed spectra.

Lowest energy Frenkel and charge transfer exciton intermixing in one-dimensional copper phthalocyanine molecular lattice

NASA Astrophysics Data System (ADS)

Bondarev, I. V.; Popescu, A.; Younts, R. A.; Hoffman, B.; McAfee, T.; Dougherty, D. B.; Gundogdu, K.; Ade, H. W.

2016-11-01

We report the results of the combined experimental and theoretical studies of the low-lying exciton states in crystalline copper phthalocyanine. We derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer exciton state and compare it with temperature dependent optical absorption spectra measured experimentally, to obtain the parameters of the Frenkel-charge-transfer exciton intermixing. The two Frenkel exciton states are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the charge transfer exciton, showing the coupling constant 0.17 eV which agrees with earlier experimental measurements. These results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines.

Preparation and magnetic properties of phthalocyanine-based carbon materials containing transition metals

NASA Astrophysics Data System (ADS)

Honda, Z.; Sato, S.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

2016-07-01

A simple method for the preparation of bulk quantities of magnetic carbon materials, which contain uniformly dispersed transition metals (M = Fe, Co, Ni, and Cu) as the magnetic components, is presented. By using highly chlorinated metal phthalocyanine as the building block and potassium as the coupling reagent, phthalocyanine-based carbon materials (PBCMs) containing transition metals were obtained. Our experiments demonstrate the structure of these PBCMs consists of transition metals embedded in graphitic carbon that includes a square planar MN4 magnetic core and the Fe and Co-PBCM possess spontaneous magnetization at room temperature. In addition, carbon-coated transition metal particles were obtained by the Wurtz-type reaction with excess amount of potassium coupling agent. The large transition metal surface area and magnetization of these M-PBCMs are useful for spintronic and catalytic applications.

Dry etching of copper phthalocyanine thin films: effects on morphology and surface stoichiometry.

PubMed

Van Dijken, Jaron G; Brett, Michael J

2012-08-24

We investigate the evolution of copper phthalocyanine thin films as they are etched with argon plasma. Significant morphological changes occur as a result of the ion bombardment; a planar surface quickly becomes an array of nanopillars which are less than 20 nm in diameter. The changes in morphology are independent of plasma power, which controls the etch rate only. Analysis by X-ray photoelectron spectroscopy shows that surface concentrations of copper and oxygen increase with etch time, while carbon and nitrogen are depleted. Despite these changes in surface stoichiometry, we observe no effect on the work function. The absorbance and X-ray diffraction spectra show no changes other than the peaks diminishing with etch time. These findings have important implications for organic photovoltaic devices which seek nanopillar thin films of metal phthalocyanine materials as an optimal structure.

Phthalocyanine identification in paintings by reflectance spectroscopy. A laboratory and in situ study

NASA Astrophysics Data System (ADS)

Poldi, G.; Caglio, S.

2013-06-01

The importance of identifying pigments using non invasive (n.i.) analyses has gained increasing importance in the field of spectroscopy applied to art conservation and art studies. Among the large set of pigments synthesized and marketed during 20th century, surely phthalocyanine blue and green pigments occupy an important role in the field of painting (including restoration) and printing, thanks to their characteristics like brightness and fastness. This research focused on the most used phthalocyanine blue (PB15:1 and PB15:3) and green pigments (PG7), and on the possibility to identify these organic compounds using a methodology like reflectance spectroscopy in the UV, visible and near IR range (UV-vis-NIR RS), performed easily through portable instruments. Laboratory tests and three examples carried out on real paintings are discussed.

Metal phthalocyanine polymers

NASA Technical Reports Server (NTRS)

Achar, B. N.; Fohlen, G. M.; Parker, J. A. (Inventor)

1984-01-01

Metal 4, 4', 4", 4"'=tetracarboxylic phthalocyanines (MPTC) are prepared by reaction of trimellitic anhydride, a salt or hydroxide of the desired metal (or the metal in powdered form), urea and a catalyst. A purer form of MPTC is prepared than heretofore. These tetracarboxylic acids are then polymerized by heat to sheet polymers which have superior heat and oxidation resistance. The metal is preferably a divalent metal having an atomic radius close to 1.35A.

Electronic structure of the organic semiconductor copper phthalocyanine: experiment and theory.

PubMed

Aristov, V Yu; Molodtsova, O V; Maslyuk, V V; Vyalikh, D V; Zhilin, V M; Ossipyan, Yu A; Bredow, T; Mertig, I; Knupfer, M

2008-01-21

The electronic structure of the organic semiconductor copper-phthalocyanine (CuPc) has been determined by a combination of conventional and resonant photoemission, near-edge x-ray absorption, as well as by the first-principles calculations. The experimentally obtained electronic valence band structure of CuPc is in very good agreement with the calculated density of states results, allowing the derivation of detailed site specific information.

Modeling the interactions of phthalocyanines in water: from the Cu(II)-tetrasulphonate to the metal-free phthalocyanine.

PubMed

Martín, Elisa I; Martínez, Jose M; Sánchez Marcos, Enrique

2011-01-14

A quantum and statistical study on the effects of the ions Cu(2+) and SO(3)(-) in the solvent structure around the metal-free phthalocyanine (H(2)Pc) is presented. We developed an ab initio interaction potential for the system CuPc-H(2)O based on quantum chemical calculations and studied its transferability to the H(2)Pc-H(2)O and [CuPc(SO(3))(4)](4-)-H(2)O interactions. The use of the molecular dynamics technique allows the determination of energetic and structural properties of CuPc, H(2)Pc, and [CuPc(SO(3))(4)](4-) in water and the understanding of the keys for the different behaviors of the three phthalocyanine (Pc) derivatives in water. The inclusion of the Cu(2+) cation in the Pc structure reinforces the appearance of two axial water molecules and second-shell water molecules in the solvent structure, whereas the presence of SO(3)(-) anions implies a well defined hydration shell of about eight water molecules around them making the macrocycle soluble in water. Debye-Waller factors for axial water molecules have been obtained in order to examine the potential sensitivity of the extended x-ray absorption fine structure technique to detect the axial water molecules.

Femtosecond to nanosecond excited state dynamics of vapor deposited copper phthalocyanine thin films.

PubMed

Caplins, Benjamin W; Mullenbach, Tyler K; Holmes, Russell J; Blank, David A

2016-04-28

Vapor deposited thin films of copper phthalocyanine (CuPc) were investigated using transient absorption spectroscopy. Exciton-exciton annihilation dominated the kinetics at high exciton densities. When annihilation was minimized, the observed lifetime was measured to be 8.6 ± 0.6 ns, which is over an order of magnitude longer than previous reports. In comparison with metal free phthalocyanine (H2Pc), the data show evidence that the presence of copper induces an ultrafast relaxation process taking place on the ca. 500 fs timescale. By comparison to recent time-resolved photoemission studies, this is assigned as ultrafast intersystem crossing. As the intersystem crossing occurs ca. 10(4) times faster than lifetime decay, it is likely that triplets are the dominant excitons in vapor deposited CuPc films. The exciton lifetime of CuPc thin films is ca. 35 times longer than H2Pc thin films, while the diffusion lengths reported in the literature are typically quite similar for the two materials. These findings suggest that despite appearing to be similar materials at first glance, CuPc and H2Pc may transport energy in dramatically different ways. This has important implications on the design and mechanistic understanding of devices where phthalocyanines are used as an excitonic material.

Functionalization of nanocrystalline diamond films with phthalocyanines

NASA Astrophysics Data System (ADS)

Petkov, Christo; Reintanz, Philipp M.; Kulisch, Wilhelm; Degenhardt, Anna Katharina; Weidner, Tobias; Baio, Joe E.; Merz, Rolf; Kopnarski, Michael; Siemeling, Ulrich; Reithmaier, Johann Peter; Popov, Cyril

2016-08-01

Phthalocyanine (Pc) derivatives containing different central metal atoms (Mn, Cu, Ti) and different peripheral chains were synthesized and comprehensively characterized. Their interaction with nanocrystalline diamond (NCD) films, as-grown by hot-filament chemical vapor deposition or after their modification with oxygen plasma to exchange the hydrogen termination with oxygen-containing groups, was studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The elemental composition as determined by XPS showed that the Pc were grafted on both as-grown and O-terminated NCD. Mn, Cu and Ti were detected together with N stemming from the Pc ring and S in case of the Ti-Pc from the peripheral ligands. The results for the elemental surface composition and the detailed study of the N 1s, S 2p and O 1s core spectra revealed that Ti-Pc grafted better on as-grown NCD but Cu-Pc and Mn-Pc on O-terminated films. Samples of Mn-Pc on as-grown and O-terminated NCD were further investigated by NEXAFS spectroscopy. The results showed ordering of the grafted molecules, laying flat on the H-terminated NCD surface while only the macrocycles were oriented parallel to the O-terminated surface with the peripheral chains perpendicular to it.

Effect of copper phthalocyanine thickness on surface morphology, optical and electrical properties of Au/CuPc/n-Si heterojunction

NASA Astrophysics Data System (ADS)

Reddy, P. R. Sekhar; Janardhanam, V.; Jyothi, I.; Harsha, Cirandur Sri; Reddy, V. Rajagopal; Lee, Sung-Nam; Won, Jonghan; Choi, Chel-Jong

2018-02-01

Effects of the thickness of copper phthalocyanine (CuPc) film (2, 5, 10, 15, 20, 30 and 40 nm) on the surface morphology, optical and electrical properties of Au/CuPc/n-Si heterojunction have been investigated. The optical band gap of CuPc film was increased with increase in the thickness of the CuPc film. The electrical properties of the Au/n-Si Schottky junction and Au/CuPc/n-Si heterojunctions were characterized by current-voltage ( I-V) and capacitance-voltage ( C-V) measurements. The barrier height, ideality factor and series resistance were estimated based on the I-V, Cheung's and Norde's methods. The barrier heights increased with increasing CuPc interlayer thickness up to 15 nm and remained constant for thickness above 20 nm, associated with the incapability of the generated carriers to reach the interface. The discrepancy in the barrier heights obtained from I-V and C-V measurements indicates the presence of barrier inhomogeneity at the interface as evidenced by higher ideality factor values. It can be concluded that the electrical properties of Au/n-Si Schottky junction can be significantly altered with the variation of CuPc thickness as interlayer.

Efficient Carbon-Based CsPbBr3 Inorganic Perovskite Solar Cells by Using Cu-Phthalocyanine as Hole Transport Material

NASA Astrophysics Data System (ADS)

Liu, Zhiyong; Sun, Bo; Liu, Xingyue; Han, Jinghui; Ye, Haibo; Shi, Tielin; Tang, Zirong; Liao, Guanglan

2018-06-01

Metal halide perovskite solar cells (PSCs) have attracted extensive research interest for next-generation solution-processed photovoltaic devices because of their high solar-to-electric power conversion efficiency (PCE) and low fabrication cost. Although the world's best PSC successfully achieves a considerable PCE of over 20% within a very limited timeframe after intensive efforts, the stability, high cost, and up-scaling of PSCs still remain issues. Recently, inorganic perovskite material, CsPbBr3, is emerging as a promising photo-sensitizer with excellent durability and thermal stability, but the efficiency is still embarrassing. In this work, we intend to address these issues by exploiting CsPbBr3 as light absorber, accompanied by using Cu-phthalocyanine (CuPc) as hole transport material (HTM) and carbon as counter electrode. The optimal device acquires a decent PCE of 6.21%, over 60% higher than those of the HTM-free devices. The systematic characterization and analysis reveal a more effective charge transfer process and a suppressed charge recombination in PSCs after introducing CuPc as hole transfer layer. More importantly, our devices exhibit an outstanding durability and a promising thermal stability, making it rather meaningful in future fabrication and application of PSCs.[Figure not available: see fulltext.

Influence of Fe3O4/Fe-phthalocyanine decorated graphene oxide on the microwave absorbing performance

NASA Astrophysics Data System (ADS)

Li, Jingwei; Wei, Junji; Pu, Zejun; Xu, Mingzhen; Jia, Kun; Liu, Xiaobo

2016-02-01

Novel graphene oxide@Fe3O4/iron phthalocyanine (GO@Fe3O4/FePc) hybrid materials were prepared through a facile one-step solvothermal method with graphene oxide (GO) sheets as template in ethylene glycol. The morphology and structure of the hybrid materials were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectrophotometer (FTIR) and X-ray diffraction (XRD), respectively. The results indicated that the monodispersed Fe3O4/FePc hybrid microspheres were uniformly self-assembled along the surface of GO sheets through electrostatic attraction and the morphology can be tuned by controlling the amount of 4,4‧-bis(3,4-dicyanophenoxy)biphenyl (BPH). As the BPH content increases, magnetization measurement of the GO@Fe3O4/FePc hybrid materials showed that the coercivity increased, while saturation magnetizations decreased. Electromagnetic properties of the hybrid materials were measured in the range of 0.5-18.0 GHz. The microwave absorbing performance enhanced with the increase of BPH content and a maximum reflection loss of -27.92 dB was obtained at 10.8 GHz when the matching thickness was 2.5 mm. Therefore, the novel electromagnetic hybrid materials can be considered as potential materials in the microwave absorbing field.

Metal phthalocyanine intermediates for the preparation of polymers

NASA Technical Reports Server (NTRS)

Achar, B. N.; Fohlen, G. M.; Parker, J. A.

1985-01-01

Metal 4, 4', 4"",-tetracarboxylic phthalocyanines (MPTC) are prepared by reaction of trimellitic anhydride, a salt or hydroxide of the desired metal (or the metal in powdered form), urea and a catalyst. A purer form of MPTC is prepared than heretofore. These tetracarboxylic acids are then polymerized by heat to sheet polymers which have superior heat and oxidation resistance. The metal is preferably a divalent metal having an atomic radius close to 1.35A.

Elaboration and use of nickel planar macrocyclic complex-based sensors for the direct electrochemical measurement of nitric oxide in biological media.

PubMed

Bedioui, F; Trevin, S; Devynck, J; Lantoine, F; Brunet, A; Devynck, M A

1997-01-01

We describe here the electrochemical detection of nitric oxide, NO, in biological systems by using chemically modified ultramicro carbon electrodes. In the first part of the paper, the different steps involved in the electrochemical preparation and characterization of the nickel-based sensor are described. This is illustrated by the use of nickel(II) tetrasulfonated phthalocyanine complex. The second part of the paper describes two examples of the direct electrochemical measurement of NO production in human blood platelets and endothelial cells from umbilical cord vein.

Characterizing the Sensitivity, Selectivity, and Reversibility of the Metal-Doped Phthalocyanine Thin-Films Used with the Interdigitated Gate Electrode Field-Effect Transistor (IGEFET) to Detect Organophosphorous Compounds and Nitrogen Dioxide

DTIC Science & Technology

1991-12-01

Susan, and my children , Abigail and Benjamin. Their love, patience, and support made the sacrifices bearable. ii Table of Contents Acknowledgements...63 e -72 -81 10 100 1000 10000 100000 1000000 Frequency (log scale) *Purge 01 a Challenge 02 (105 Porn Boron Trifluoride) ePurge #2 Figure C-85. Phase... porn Ammonia) * Purge #2 Figure D-85.Gatin versus Frequency Response of IGEFET Microsensor for it Series of Room Air Purges and Challenge Gas Exposures

Graphene-enhanced intermolecular interaction at interface between copper- and cobalt-phthalocyanines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dou, Wei-Dong; Center of Super-Diamond and Advanced Films; Huang, Shu-Ping

2015-10-07

Interfacial electronic structures of copper-phthalocyanine (CuPc), cobalt-phthalocyanine (CoPc), and graphene were investigated experimentally by using photoelectron spectroscopy. While the CuPc/graphene interface shows flat band structure and negligible interfacial dipole indicating quite weak molecule-substrate interaction, the CuPc/CoPc/graphene interface shows a large interfacial dipole and obvious energy level bending. Controlled experiments ruled out possible influences from the change in film structure of CuPc and pure π–π interaction between CoPc and CuPc. Analysis based on X-ray photoelectron spectroscopy and density functional theory reveals that the decrease in the work function for the CuPc/CoPc/graphene system is induced by the intermolecular interaction between CuPc andmore » CoPc which is enhanced owning to the peculiar electronic properties at the CoPc-graphene interface.« less

Electronic structures and magnetic/optical properties of metal phthalocyanine complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baba, Shintaro; Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.jp; Oku, Takeo

2016-02-01

Electronic structures and magnetic / optical properties of metal phthalocyanine complexes were studied by quantum calculations using density functional theory. Effects of central metal and expansion of π orbital on aromatic ring as conjugation system on the electronic structures, magnetic, optical properties and vibration modes of infrared and Raman spectra of metal phthalocyanines were investigated. Electron and charge density distribution and energy levels near frontier orbital and excited states were influenced by the deformed structures varied with central metal and charge. The magnetic parameters of chemical shifts in {sup 13}C-nuclear magnetic resonance ({sup 13}C-NMR), principle g-tensor, A-tensor, V-tensor of electricmore » field gradient and asymmetry parameters derived from the deformed structures with magnetic interaction of nuclear quadruple interaction based on electron and charge density distribution with a bias of charge near ligand under crystal field.« less

Depopulation of Single-Phthalocyanine Molecular Orbitals upon Pyrrolic-Hydrogen Abstraction on Graphene.

PubMed

Néel, Nicolas; Lattelais, Marie; Bocquet, Marie-Laure; Kröger, Jörg

2016-02-23

Single-molecule chemistry with a scanning tunneling microscope has preponderantly been performed on metal surfaces. The molecule-metal hybridization, however, is often detrimental to genuine molecular properties and obscures their changes upon chemical reactions. We used graphene on Ir(111) to reduce the coupling between Ir(111) and adsorbed phthalocyanine molecules. By local electron injection from the tip of a scanning tunneling microscope the two pyrrolic H atoms were removed from single phthalocyanines. The detachment of the H atom pair induced a strong modification of the molecular electronic structure, albeit with no change in the adsorption geometry. Spectra and maps of the differential conductance combined with density functional calculations unveiled the entire depopulation of the highest occupied molecular orbital upon H abstraction. Occupied π states of intact molecules are proposed to be emptied via intramolecular electron transfer to dangling σ states of H-free N atoms.

Cyclic Tetrapyrrole Sulfonation, Metals, and Oligomerization in Antiprion Activity▿

PubMed Central

Caughey, Winslow S.; Priola, Suzette A.; Kocisko, David A.; Raymond, Lynne D.; Ward, Anne; Caughey, Byron

2007-01-01

Cyclic tetrapyrroles are among the most potent compounds with activity against transmissible spongiform encephalopathies (TSEs; or prion diseases). Here the effects of differential sulfonation and metal binding to cyclic tetrapyrroles were investigated. Their potencies in inhibiting disease-associated protease-resistant prion protein were compared in several types of TSE-infected cell cultures. In addition, prophylactic antiscrapie activities were determined in scrapie-infected mice. The activity of phthalocyanine was relatively insensitive to the number of peripheral sulfonate groups but varied with the type of metal bound at the center of the molecule. The tendency of the various phthalocyanine sulfonates to oligomerize (i.e., stack) correlated with anti-TSE activity. Notably, aluminum(III) phthalocyanine tetrasulfonate was both the poorest anti-TSE compound and the least prone to oligomerization in aqueous media. Similar comparisons of iron- and manganese-bound porphyrin sulfonates confirmed that stacking ability correlates with anti-TSE activity among cyclic tetrapyrroles. PMID:17709470

Soluble copper phthalocyanine applied for organic solar cells.

PubMed

Zhang, Tianhui; Piao, Lingyu; Zha, Suling; Jiang, Chao; Xu, Zheng; Gao, Liyan; Wu, Qian; Kong, Chao

2011-11-01

A soluble derivative of copper phthalocyanine, that is 2,9,16,23-tetra carboxyl copper phthalocyanine (CuTCPc), is synthesized in this paper. The applications of CuTCPc as donor and interlayer materials in solar cell devices are investigated. The results demonstrate that when CuTCPc is used as a donor material, the performance of the device ITO/CuTCPc/PCBM/Al shows an open circuit voltage (V(OC)) of 0.54 V, a short circuit current (J(SC)) of 0.825 mA/cm2, a fill factor (FF) of 32.3% and the power conversion efficiency (nu) of 0.14%. When CuTCPc acts as an interlayer, the performance of the device ITO/CuTCPc/P3HT:PCBM/Al is improved: J(SC) increases to 3.12 mA/cm2, V(OC) increases to 0.59 V, FF increases to 33.8%, and the corresponding nu is 0.62%.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis.

PubMed

Gan, Patrick; Foord, John S; Compton, Richard G

2015-10-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.

Organic photovoltaic devices comprising solution-processed substituted metal-phthalocyanines and exhibiting near-IR photo-sensitivity

DOEpatents

McGrath, Dominic V.; Mayukh, Mayank; Placencia, Diogenes; Armstrong, Neal R.

2016-11-29

Organic photovoltaic (OPV) devices are disclosed. An exemplary device has first and second electrodes and an organic, photovoltaically active zone located between the first and second electrodes. The photovoltaically active zone includes an organic electron-donor material and an organic electron-acceptor material. The electron-donor material includes one or more trivalent- or tetravalent-metal phthalocyanines with alkylchalcogenide ring substituents, and is soluble in at least one organic solvent. This solubility facilitates liquid-processability of the donor material, including formation of thin-films, on an unlimited scale to form planar and bulk heterojunctions in organic OPVs. These donor materials are photovoltaically active in both visible and near-IR wavelengths of light, enabling more of the solar spectrum, for example, to be applied to producing electricity. Also disclosed are methods for producing the metalated phthalocyanines and actual devices.

Synthesis of new porphyrinoids for biomedical and materials applications

NASA Astrophysics Data System (ADS)

Stewart, Fraser

The facile synthesis of three non-hydrolysable thioglycosylated porphyrinoids is reported. Starting from meso perfluorophenylporphyrin (TPPF20), the non-hydrolysable thioglycosylated porphyrin (PGlc4), chlorin (CGlc4), isobacteriochlorin (IGlc4), and bacteriochlorin (BGlc4) can be made in 2-3 steps. The ability to append a wide range of targeting agents onto the perfluorophenyl moieties, the chemical stability, and the ability to fine-tune the photophysical properties of the chromophores make this a suitable platform for development of biochemical tags, diagnostics, or as photodynamic therapeutic agents. With reduction of one or two pyrrole double bonds, there is a red shift in the lowest energy absorption band and a significant increase in intensity. The fluorescence of these porphyrinoids is in the order PGlc4 = BGlc4 < CGlc4 < IGlc4 and there is a corresponding decrease in the amount of triplet formed. Fluorescence micrographs of cells after treatment with these four porphyrinoids indicate they are taken up. The CGlc4 and IGlc4 may be dual function agents that can detect cancer by luminescence, and treat cancer by photodynamic therapy (PDT). Porphyrins appended with four rigid hydrogen bonding motifs on the meso positions were synthesized and self-assembled into a cofacial cage with four complementary bis- (decyl)melamine units in dry solvents, these hydrogen-bonded cages were analysed by diffusion-ordered spectroscopy (DOSY) in solution. The hydrocarbon chains on the melamine mediate the formation of nanofilms on surfaces as the solvent slowly evaporates. A water soluble zinc (II) phthalocyanine symmetrically appended with eight thioglucose units was synthesized from commercially available hexadecafluoro-phthalocyaninato zinc(II) by controlled nucleophilic substitution of the peripheral fluoro groups by thio-sugars. The photophysical properties and cancer cell uptake studies of this nonhydrolyzable thioglycosylated phthalocyanine are reported. The new compound has amphiphilic character, is chemically and photochemically stable, and can potentially be used as a photosensitizer in photodynamic therapy. A porphyrin bearing pyridyl groups at the meso positions was synthesized using 2,6-diacetamido-4-formylpyridine. A new method has been developed for the synthesis of the precursor aldehyde that avoid much of the problems associated with the earlier synthesis. With this porphyrin it is possible to build hetero-complementary rigid, multi-porphyrin supramolecular arrays via hydrogen bonds. For example, when using naphthalenediimide (NDI) units a checkerboard pattern is expected to be formed using this porphyrin as a donor and NDI as an acceptor where triple hydrogen bond is formed between the diimide and pyridyl units. Energy transfer can be studied through this hydrogen bonded supramolecular assembly. The synthesis of a triply bridged diporphyrin appended with six thioglucose units is reported. The electronic spectrum of this triply bridged porphyrin has enhanced intensity at low-energy wavelengths that reaches the near infrared region. The goal of this project is to create tumor targeting dyes that can be activated with red wavelengths of light that penetrate deeper into tissues. This new compound is amphiphilic in nature, chemically and photochemically stable, expected to have unusual photophysical and electrochemical properties, and can potentially be used as a photosensitizer in photodynamic therapy.

Some Phthalocyanine and Naphthalocyanine Derivatives as Corrosion Inhibitors for Aluminium in Acidic Medium: Experimental, Quantum Chemical Calculations, QSAR Studies and Synergistic Effect of Iodide Ions.

PubMed

Dibetsoe, Masego; Olasunkanmi, Lukman O; Fayemi, Omolola E; Yesudass, Sasikumar; Ramaganthan, Baskar; Bahadur, Indra; Adekunle, Abolanle S; Kabanda, Mwadham M; Ebenso, Eno E

2015-08-28

The effects of seven macrocyclic compounds comprising four phthalocyanines (Pcs) namely 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (Pc1), 2,3,9,10,16,17,23,24-octakis(octyloxy)-29H,31H-phthalocyanine (Pc2), 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (Pc3) and 29H,31H-phthalocyanine (Pc4), and three naphthalocyanines namely 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (nPc1), 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (nPc2) and 2,3-naphthalocyanine (nP3) were investigated on the corrosion of aluminium (Al) in 1 M HCl using a gravimetric method, potentiodynamic polarization technique, quantum chemical calculations and quantitative structure activity relationship (QSAR). Synergistic effects of KI on the corrosion inhibition properties of the compounds were also investigated. All the studied compounds showed appreciable inhibition efficiencies, which decrease with increasing temperature from 30 °C to 70 °C. At each concentration of the inhibitor, addition of 0.1% KI increased the inhibition efficiency compared to the absence of KI indicating the occurrence of synergistic interactions between the studied molecules and I(-) ions. From the potentiodynamic polarization studies, the studied Pcs and nPcs are mixed type corrosion inhibitors both without and with addition of KI. The adsorption of the studied molecules on Al surface obeys the Langmuir adsorption isotherm, while the thermodynamic and kinetic parameters revealed that the adsorption of the studied compounds on Al surface is spontaneous and involves competitive physisorption and chemisorption mechanisms. The experimental results revealed the aggregated interactions between the inhibitor molecules and the results further indicated that the peripheral groups on the compounds affect these interactions. The calculated quantum chemical parameters and the QSAR results revealed the possibility of strong interactions between the studied inhibitors and metal surface. QSAR analysis on the quantum chemical parameters obtained with B3LYP/6-31G (d,p) method show that a combination of two quantum chemical parameters to form a composite index provides the best correlation with the experimental data.

Spectroscopic insights on selfassembly and excited state interactions between rhodamine and phthalocyanine molecules.

PubMed

Geng, Hao; Zhang, Xian-Fu

2015-03-15

The absorption and fluorescence spectra as well as fluorescence lifetimes of tetrasulfonated zinc phthalocyanine ZnPc(SO3Na)4 were measured in the absence and presence of four rhodamine dyes, Rhodamine B (RB), Ethyl rhodamine B (ERB), Rhodamine 6G (R6G), Rhodamine 110 (R110), and Pyronine B (PYB). The ground state complexes of phthalocyanine-(Rhodamine)2 were observed which exhibit new absorption bands. The binding constants are all very large (0.86×10(5)-0.22×10(8) M(-1)), suggesting rhodamine-phthalocyanine pairs are very good combinations for efficient selfassembly. Both the fluorescence intensity and the lifetime values of ZnPc(SO3Na)4 were decreased by the presence of rhodamines. The structural effect of rhodamines on selfassembly is significant. The ground state binding and dynamic quenching capability is PYB>R6G>ERB>RB>R110. The dynamic fluorescence quenching is due to the photoinduced electron transfer (PET). The PET rate constant is very large and in the order of 10(13) M(-1) s(-1), much greater than kf and kic (in the order of 10(8) M(-1) s(-1)), which means that the PET efficiency is almost 100%. Therefore the non-covalent Pc-rhodamine is a very good pair of donor/acceptor for potential efficient solar energy conversion. Copyright © 2014 Elsevier B.V. All rights reserved.

Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

Edge-on and face-on functionalized Pc on enriched semiconducting SWCNT hybrids.

PubMed

Arellano, Luis M; Martín-Gomis, Luis; Gobeze, Habtom B; Molina, Desiré; Hermosa, Cristina; Gómez-Escalonilla, María J; Fierro, José Luis G; Sastre-Santos, Ángela; D'Souza, Francis; Langa, Fernando

2018-03-15

Enriched semiconducting single-walled carbon nanotubes (SWCNT (6,5) and SWCNT (7,6)) and HiPco nanotubes were covalently functionalized with either zinc phthalocyanine or silicon phthalocyanine as electron donors. The synthetic strategy resulted in edge-on and face-on geometries with respect to the phthalocyanine geometry, with both phthalocyanines held by an electronically conducting diphenylacetylene linker. The extent of functionalization in the MPc-SWCNT (M = Zn or Si) donor-acceptor nanohybrids was determined by systematic studies involving AFM, TGA, XPS, optical and Raman techniques. Intramolecular interactions in MPc-SWCNT nanohybrids were probed by studies involving optical absorbance, Raman, luminescence and electrochemical studies. Different degrees of interactions were observed depending on the type of MPc and mode of attachment. Substantial quenching of MPc fluorescence in these hybrids was observed from steady-state and three-dimensional fluorescence mapping, which suggests the occurrence of excited state events. Evidence for the occurrence of excited state charge transfer type interactions was subsequently secured from femtosecond transient absorption studies covering both the visible and near-infrared regions. Furthermore, electron-pooling experiments performed in the presence of a sacrificial electron donor and a second electron acceptor revealed accumulation of one-electron reduced product upon continuous irradiation of the nanohybrids. In such experiments, the ZnPc-SWCNT (6,5) nanohybrid outperformed other nanohybrids and this suggests that this is a superior donor-acceptor system for photocatalytic applications.

Phthalocyanines And Their Sulfonated Derivatives As Photosensitizers In Photodynamic Therapy.

NASA Astrophysics Data System (ADS)

Riesz, Peter; Krishna, C. Murali

1988-02-01

Photodynamic therapy (PDT) of human tumors with hematoporphyrin derivative (HpD) has achieved encouraging results. However, HpD is a complex mixture whose composition varies in different preparations and with time of storage. The future promise of PDT for cancer treatment depends on the development of new chemically defined sensitizers which absorb more strongly than HpD in the 600-800 nm region. A shift to higher wavelengths is desirable since it allows increased light penetration in human tissues. In vivo, these sensitizers should be non-toxic, localize selectively in tumors and generate cytotoxic species upon illumination with a high quantum yield. These damaging species may be singlet oxygen (1O2) produced by the transfer of energy from the triplet state of the sensitizer to oxygen (Type II) or superoxide anion radicals formed by electron transfer to oxygen or substrate radicals generated by electron or hydrogen transfer directly from the sensitizer (Type I). The recent work of several groups indicating that phthalocyanines and their water soluble derivatives are promising candidates for PDT is reviewed. The photophysics, photochemistry, photosensitized killing of cultured mammalian cells and the use for in vivo photodynamic therapy of phthalocyanines is outlined. Our studies of the post-illumination photohemolysis of human red blood cells as a model system for membrane photomodification sensitized by phthalocyanine sulfonates are consistent with the predominant role of 1O2 as the damaging species.

Photooxidation of d(TpG) by phthalocyanines and riboflavin. Isolation and characterization of dinucleoside monophosphates containing the 4R* and 4S* diastereoisomers of 4,8-dihydro-4-hydroxy-8-oxo-2'-deoxy-guanosine.

PubMed Central

Buchko, G W; Cadet, J; Berger, M; Ravanat, J L

1992-01-01

Phthalocyanine mediated photosensitization of 2'-deoxyguanosine (dG) in oxygen saturated aqueous solution has previously been shown to result in the addition of molecular oxygen to the guanine base generating the 4R* and 4S* diastereoisomers of 4,8-dihydro-4-hydroxy-8-oxo-2'-deoxyguanosine (dO) (the asterisk denotes unambiguous assignment of the 4R and 4S diastereoisomers). The data presented here show that the same guanine modified bases are generated in a 1:1 ratio when thymidylyl-(3',5')-2'-deoxyguanosine (d(TpG)) is similarly photo-oxidized. These modified dinucleoside monophosphates, labelled d(TpO)-A and -B, have been isolated by high performance liquid chromatography and characterized by proton NMR spectrometry, fast atom bombardment mass spectrometry, and enzymatic digestions. Photosensitization in D2O instead of H2O leads to an increase in the rate of d(TpO) formation that is consistent with a type II (singlet oxygen) reaction mechanism. Three interesting properties of these modified dinucleoside monophosphates are: i) the rate of their digestion with spleen phosphodiesterase is greatly reduced relative to d(TpG), ii) they are not digested by snake venom phosphodiesterase, and iii) they are stable to 1.0 M piperidine at 90 degrees C for 30 min. The latter observation indicates that 4,8-dihydro-4-hydroxy-8-oxoguanine is not a base lesion responsible for the strand breaks observed following hot piperidine treatment of DNA exposed to type II photosensitizers or chemically generated singlet oxygen. PMID:1329029

Disulfide-Linked Dendritic Oligomeric Phthalocyanines as Glutathione-Responsive Photosensitizers for Photodynamic Therapy.

PubMed

Chow, Sun Y S; Wong, Roy C H; Zhao, Shirui; Lo, Pui-Chi; Ng, Dennis K P

2018-04-17

A series of disulfide-linked dendritic phthalocyanines were synthesized by using the Cu I -catalyzed alkyne-azide cycloaddition reaction as the key step. Whereas these compounds were essentially nonaggregated in N,N-dimethylformamide, they were stacked in citrate solution (pH 7.4, with 1 % Cremophor EL), as shown by the broad appearance of their Q-band absorption. Having two-to-six zinc(II) phthalocyanine units in a molecule, these compounds were significantly self-quenched, particularly in citrate solution. Both the fluorescence intensity and singlet-oxygen generation efficiency were significantly lower than those of the monomeric counterparts, and the self-quenching efficiency increased as the number of phthalocyanine units increased. Upon interaction with 5 mm glutathione (GSH) in citrate solution, the fluorescence intensity of these compounds increased as a result of cleavage of the disulfide linkages and separation of the phthalocyanine units, which thereby reduced the self-quenching effect. The "on/off" ratios were found to be 7, 18, 23, and 21 for the dimeric (PC2), trimeric (PC3), tetrameric (PC4), and hexameric (PC6) systems, respectively. GSH also enhanced the fluorescence emission inside human colon adenocarcinoma HT29 cells and promoted the formation of singlet oxygen of these compounds. Upon irradiation, their half maximal inhibitory concentration (IC 50 ) values were found to be in the range of 0.18 to 0.38 μm. Finally, the biodistribution and activation of PC2 and PC6 were also examined in HT29 tumor-bearing nude mice. For both compounds, the fluorescence intensity per unit area at the tumor was found to grow gradually during the first 24 h. Whereas the intensity then dropped for PC2, the intensity for PC6 remained steady over the following 6 d, which might have been a result of the enhanced permeability and retention effect arising from the larger molecular mass of the hexameric system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carotenoid Photoprotection in Artificial Photosynthetic Antennas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kloz, Miroslav; Pillai, Smitha; Kodis, Gerdenis

A series of phthalocyanine-carotenoid dyads in which a phenylamino group links a phthalocyanine to carotenoids having 8-11 backbone double bonds were examined by visible and near-infrared femtosecond pump-probe spectroscopy combined with global fitting analysis. The series of molecules has permitted investigation of the role of carotenoids in the quenching of excited states of cyclic tetrapyrroles. The transient behavior varied dramatically with the length of the carotenoid and the solvent environment. Clear spectroscopic signatures of radical species revealed photoinduced electron transfer as the main quenching mechanism for all dyads dissolved in a polar solvent (THF), and the quenching rate was almostmore » independent of carotenoid length. However, in a nonpolar solvent (toluene), quenching rates displayed a strong dependence on the conjugation length of the carotenoid and the mechanism did not include charge separation. The lack of any rise time components of a carotenoid S 1 signature in all experiments in toluene suggests that an excitonic coupling between the carotenoid S 1 state and phthalocyanine Q state, rather than a conventional energy transfer process, is the major mechanism of quenching. A pronounced inhomogeneity of the system was observed and attributed to the presence of a phenyl-amino linker between phthalocyanine and carotenoids. On the basis of accumulated work on various caroteno-phthalocyanine dyads and triads, we have now identified three mechanisms of tetrapyrrole singlet excited state quenching by carotenoids in artificial systems: (i) Car-Pc electron transfer and recombination; (ii) 1Pc to Car S 1 energy transfer and fast internal conversion to the Car ground state; (iii) excitonic coupling between 1Pc and Car S 1 and ensuing internal conversion to the ground state of the carotenoid. The dominant mechanism depends upon the exact molecular architecture and solvent environment. These synthetic systems are providing a deeper understanding of structural and environmental effects on the interactions between carotenoids and tetrapyrroles and thereby better defining their role in controlling natural photosynthetic systems.« less

Structure-matched Phthalocyanine Ion Pair as a Red-emitting Fluorescent Optical Probe for the Analysis of Sodium Dodecylbenzenesulfonate with High Specificity and Sensitivity.

PubMed

Yu, Fei; Guo, Menglin; Deng, Yabin; Lu, Yin; Chen, Lin; Huang, Ping; Li, Donghui

2016-01-01

We have found that a positively charged cationic copper phthalocyanine, Alcian blue (Alcian blue 8GX), can efficiently quench the fluorescence of an oppositely charged red fluorescent phthalocyanine compound with a matched molecular structure, tetrasulfonated aluminum phthalocyanine (AlS4Pc), because of the formation of an ion pair complex (AlS4Pc-Alcian blue 8GX) that exhibits almost no fluorescence. An investigation was carried out on the fluorescence recovery of AlS4Pc-Alcian blue 8GX caused by a series of anionic surfactants containing a sulfonic group (sodium dodecylbenzenesulfonate (SDBS), sodium lauryl sulfate (SLS), and sodium dodecyl sulfate (SDS)). The results showed that SDBS exhibited a significant response, and the highest sensitivity among the surfactants. Due to its high efficiency of fluorescence quenching and the high level of fluorescence recovery, direct observes can even be performed by the naked eye. The results revealed that the Alcian blue 8GX-AlS4Pc ion-pair complex fluorescent probe only responded to SDBS in the low-concentration range. Based on the new founding, this study proposed a novel principle and method of fluorescence enhancement to specifically measure the concentration of SDBS, thereby achieving a highly sensitive and highly specific determination of SDBS. Under the optimal conditions, the fluorescence intensity (I(f)) of the system and the concentration of SDBS in the range of 1 × 10(-7) - 1 × 10(-5) mol/dm(3) exhibited a good linear relationship. This method is highly sensitive, and the operation is simple and rapid. It had been applied for the quantitative analysis of SDBS in environmental water, while achieving satisfactory results compared with those of the standard method. This study developed a new application of the fluorescent phthalocyanine compounds used as molecular probes in analytical sciences.

Optical Absorption and Visible Photoluminescence from Thin Films of Silicon Phthalocyanine Derivatives

PubMed Central

Rodríguez Gómez, Arturo; Moises Sánchez-Hernández, Carlos; Fleitman-Levin, Ilán; Arenas-Alatorre, Jesús; Carlos Alonso-Huitrón, Juan; Elena Sánchez Vergara, María

2014-01-01

The interest of microelectronics industry in new organic compounds for the manufacture of luminescent devices has increased substantially in the last decade. In this paper, we carried out a study of the usage feasibility of three organic bidentate ligands (2,6-dihydroxyanthraquinone, anthraflavic acid and potassium derivative salt of anthraflavic acid) for the synthesis of an organic semiconductor based in silicon phthalocyanines (SiPcs). We report the visible photoluminescence (PL) at room temperature obtained from thermal-evaporated thin films of these new materials. The surface morphology of these films was analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). AFM indicated that the thermal evaporation technique is an excellent resource in order to obtain low thin film roughness when depositing these kinds of compounds. Fourier transform infrared spectroscopy (FTIR) spectroscopy was employed to investigate possible changes in the intra-molecular bonds and to identify any evidence of crystallinity in the powder compounds and in the thin films after their deposition. FTIR showed that there was not any important change in the samples after the thermal deposition. The absorption coefficient (α) in the absorption region reveals non-direct transitions. Furthermore, the PL of all the investigated samples were observed with the naked eye in a bright background and also measured by a spectrofluorometer. The normalized PL spectra showed a Stokes shift ≈ 0.6 eV in two of our three samples, and no PL emission in the last one. Those results indicate that the Vis PL comes from a recombination of charge carriers between conduction band and valence band preceded by a non-radiative relaxation in the conduction band tails. PMID:28788200

Facile synthesis of ZnPc nanocubes: An electron emitting material for field emission display devices

NASA Astrophysics Data System (ADS)

Samanta, M.; Ghorai, U. K.; Mukherjee, M.; Howli, P.; Chattopadhyay, K. K.

2017-05-01

A simple low temperature water chemical route for synthesizing Zinc Phthalocyanine (ZnPc) nanostructures were reported here. The as-prepared samples were well analysed by X-ray diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM) technique. The plausible formation mechanism of cube like nanostructures was also explained here. Cold cathode emission properties of ZnPc nanocubes were studied by using an indigenously designed high vacuum system at anode to cathode distance 130 µm. The turn on field and enhancement factor is found to be 5.0 V/μm @ 1µA/cm2 and 1757 respectively. Cold cathode emission properties were further investigated theoretically by finite element method using ANSYS Maxwell simulation package. The obtained results strongly professed that ZnPc nanocubes can act as potential candidate for electron emitter for field emission display devices and many more.

Phthalocyanine adsorption to graphene on Ir(111): Evidence for decoupling from vibrational spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Endlich, M., E-mail: michael.endlich@tu-ilmenau.de; Gozdzik, S.; Néel, N.

2014-11-14

Phthalocyanine molecules have been adsorbed to Ir(111) and to graphene on Ir(111). From a comparison of scanning tunneling microscopy images of individual molecules adsorbed to the different surfaces alone it is difficult to discern potential differences in the molecular adsorption geometry. In contrast, vibrational spectroscopy using inelastic electron scattering unequivocally hints at strong molecule deformations on Ir(111) and at a planar adsorption geometry on graphene. The spectroscopic evidence for the different adsorption configurations is supported by density functional calculations.

Visible light detoxification by 2,9,16,23-tetracarboxyl phthalocyanine copper modified amorphous titania

NASA Astrophysics Data System (ADS)

Chen, Feng; Deng, Zhigang; Li, Xiaopei; Zhang, Jinlong; Zhao, Jincai

2005-10-01

Visible light detoxification of methyl orange (MO) was achieved with a photo-stable 2,9,16,23-tetracarboxyl phthalocyanine (TcPc)/amorphous TiO 2 hybrid photocatalyst. TcPc/amorphous TiO 2 exhibits an excellent photocatalytic activity under visible irradiation ( λ > 550 nm). Besides the active oxygen species, sensitizer radical cation, TcPc + rad , was also found to react with MO directly and induce the photodegradation of MO significantly for the first time in dye sensitized photocatalytic system.

Oxygen reduction reaction properties of nitrogen-incorporated nanographenes synthesized using in-liquid plasma from mixture of ethanol and iron phthalocyanine

NASA Astrophysics Data System (ADS)

Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

2018-04-01

Nanographenes were synthesized using in-liquid plasma from a mixture of iron phthalocyanine and ethanol. In a previous study, micrometer-scale flakes with nitrogen incorporation were obtained. A nonprecious metal catalytic activity was observed with 3.13 electrons in an oxygen reduction reaction under an acidic solute condition. Large-surface-area, high-graphene-crystallinity, and iron-carbon-bonding sites were found owing to a high catalytic activity in Fe-N/nanographene.

Copper-phthalocyanine based metal-organic interfaces: the effect of fluorination, the substrate, and its symmetry.

PubMed

de Oteyza, D G; El-Sayed, A; Garcia-Lastra, J M; Goiri, E; Krauss, T N; Turak, A; Barrena, E; Dosch, H; Zegenhagen, J; Rubio, A; Wakayama, Y; Ortega, J E

2010-12-07

Metal-organic interfaces based on copper-phthalocyanine monolayers are studied in dependence of the metal substrate (Au versus Cu), of its symmetry [hexagonal (111) surfaces versus fourfold (100) surfaces], as well as of the donor or acceptor semiconducting character associated with the nonfluorinated or perfluorinated molecules, respectively. Comparison of the properties of these systematically varied metal-organic interfaces provides new insight into the effect of each of the previously mentioned parameters on the molecule-substrate interactions.

Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glaser, Mathias; Peisert, Heiko, E-mail: heiko.peisert@uni-tuebingen.de; Adler, Hilmar

2015-03-14

The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the chargemore » transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.« less

Ultralong copper phthalocyanine nanowires with new crystal structure and broad optical absorption.

PubMed

Wang, Hai; Mauthoor, Soumaya; Din, Salahud; Gardener, Jules A; Chang, Rio; Warner, Marc; Aeppli, Gabriel; McComb, David W; Ryan, Mary P; Wu, Wei; Fisher, Andrew J; Stoneham, Marshall; Heutz, Sandrine

2010-07-27

The development of molecular nanostructures plays a major role in emerging organic electronic applications, as it leads to improved performance and is compatible with our increasing need for miniaturization. In particular, nanowires have been obtained from solution or vapor phase and have displayed high conductivity or large interfacial areas in solar cells. In all cases however, the crystal structure remains as in films or bulk, and the exploitation of wires requires extensive postgrowth manipulation as their orientations are random. Here we report copper phthalocyanine (CuPc) nanowires with diameters of 10-100 nm, high directionality, and unprecedented aspect ratios. We demonstrate that they adopt a new crystal phase, designated eta-CuPc, where the molecules stack along the long axis. The resulting high electronic overlap along the centimeter length stacks achieved in our wires mediates antiferromagnetic couplings and broadens the optical absorption spectrum. The ability to fabricate ultralong, flexible metal phthalocyanine nanowires opens new possibilities for applications of these simple molecules.

Analyte chemisorption and sensing on n- and p-channel copper phthalocyanine thin-film transistors.

PubMed

Yang, Richard D; Park, Jeongwon; Colesniuc, Corneliu N; Schuller, Ivan K; Royer, James E; Trogler, William C; Kummel, Andrew C

2009-04-28

Chemical sensing properties of phthalocyanine thin-film transistors have been investigated using nearly identical n- and p-channel devices. P-type copper phthalocyanine (CuPc) has been modified with fluorine groups to convert the charge carriers from holes to electrons. The sensor responses to the tight binding analyte dimethyl methylphosphonate (DMMP) and weak binding analyte methanol (MeOH) were compared in air and N(2). The results suggest that the sensor response involves counterdoping of pre-adsorbed oxygen (O(2)). A linear dependence of chemical response to DMMP concentration was observed in both n- and p- type devices. For DMMP, there is a factor of 2.5 difference in the chemical sensitivity between n- and p-channel CuPc thin-film transistors, even though it has similar binding strength to n- and p-type CuPc molecules as indicated by the desorption times. The effect is attributed to the difference in the analyte perturbation of electron and hole trap energies in n- and p-type materials.

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films

NASA Astrophysics Data System (ADS)

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J.; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G.; Headrick, Randall L.; McGill, Stephen A.; Furis, Madalina I.

2015-11-01

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ - d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of -4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials.

Spectroscopic investigation on the interaction of copper porphyrazines and phthalocyanine with human telomeric G-quadruplex DNA.

PubMed

Hassani, Leila; Hakimian, Fatemeh; Safaei, Elham

2014-01-01

The G-quadruplex DNA is a novel target for anticancer drug discovery and many scientific groups are investigating interaction of small molecules with G-quadruplex DNA to discover therapeutic agents for cancer. Here, interaction of a phthalocyanine (Cu(PcTs)) and two tetrapyridinoporphyrazines ([Cu(2,3-tmtppa)](4+) and [Cu(3,4-tmtppa)](4+)) with Na(+) and K(+) forms of human telomeric G-quadruplex DNA has been investigated by spectroscopic techniques. The results indicated that interaction of the cationic porphyrazines is remarkably stronger than the anionic phthalocyanine and they presumably bind to the G-quadruplex DNA through end-stacking. Fluorescent intercalator displacement assay implied the displacement ability of the complexes with thiazole orange. In addition, circular dichroism spectra of both quadruplex forms converge to the Na(+) isoform after binding to the porphyrazines. In conclusion, the porphyrazines as the complexes that bind to the G-quadruplex DNA, could be suitable candidates for further investigations about inhibition of telomerase enzyme. Copyright © 2013 Elsevier B.V. All rights reserved.

Electron-transfer quenching vs. exciplex-mediated quenching of the low-lying excited states in phthalocyanines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prasad, D.R.; Ferraudi, G.

1983-05-25

Oxidative electron-transfer quenching of the lowest ligand-centered /sup 3/..pi pi..* of ruthenium (RU) phthalocyanines (pc)L/sub 2/, L = dimethylformamide (dmf) or pyridine (py), by a series of nitroaromatic compounds, viologen salts, and metal complexes has been investigated by laser and conventional flash photolysis. The quenching rate constants, treated according to Marcus-Hush and Rehm-Weller equations, gave self-exchange rate constants, k/sub exch/ approx. 10/sup 7/ M/sup -1/ s/sup -1/, for the electron exchange between the /sup 3/..pi pi..* and the ruthenium(II) ligand radical. The excited states of a number of phthalocyanines, e.g. Ru(pc)(dimethyl sulfoxide(Me/sub 2/SO)/sub 2/), Ru(pc)(dmf)CO, Ru(pc)(py)CO, and Rh(pc)(methanol(CH/sub 3/OH)chloride), undergomore » quenching mediated by exciplex formation. The formation of exciplexes is discussed in terms of the related exciplexes of the porphyrins.« less

Biological activities of phthalocyanines. XIV. Effect of hydrophobic phthalimidomethyl groups on the in vivo phototoxicity and mechanism of photodynamic action of sulphonated aluminium phthalocyanines.

PubMed Central

Boyle, R. W.; Paquette, B.; van Lier, J. E.

1992-01-01

Aluminium phthalocyanines substituted to different degrees with hydrophilic sulphonic acid and hydrophobic phthalimidomethyl groups were investigated in vivo as new agents for the photodynamic therapy of malignant tumours. Parameters studied included the photodynamic action on EMT-6 mammary tumours in BALB/c mice, the therapeutic window and the potential for direct cell killing, assayed via an in vivo/in vitro test. Although the efficiency of photoinactivation of the EMT-6 tumour increases by a factor of ten with reduction of the number of sulphonic acid groups from four to two, no further effect was seen with the addition of the hydrophobic phthalimidomethyl groups. Addition of the latter groups however increased the potential for direct cell killing by a factor of two and expanded the therapeutic window by a factor of four, thus improving the usefulness of the dye as a photosensitiser for the photodynamic therapy of cancer. PMID:1616852

Chemically Reversible Reactions of Hydrogen Sulfide with Metal Phthalocyanines

PubMed Central

2015-01-01

Hydrogen sulfide (H2S) is an important signaling molecule that exerts action on various bioinorganic targets. Despite this importance, few studies have investigated the differential reactivity of the physiologically relevant H2S and HS– protonation states with metal complexes. Here we report the distinct reactivity of H2S and HS– with zinc(II) and cobalt(II) phthalocyanine (Pc) complexes and highlight the chemical reversibility and cyclability of each metal. ZnPc reacts with HS–, but not H2S, to generate [ZnPc-SH]−, which can be converted back to ZnPc by protonation. CoPc reacts with HS–, but not H2S, to form [CoIPc]−, which can be reoxidized to CoPc by air. Taken together, these results demonstrate the chemically reversible reaction of HS– with metal phthalocyanine complexes and highlight the importance of H2S protonation state in understanding the reactivity profile of H2S with biologically relevant metal scaffolds. PMID:24785654

Modification of symmetrically substituted phthalocyanines using click chemistry: phthalocyanine nanostructures by nanoimprint lithography.

PubMed

Chen, Xiaochun; Thomas, Jayan; Gangopadhyay, Palash; Norwood, Robert A; Peyghambarian, N; McGrath, Dominic V

2009-09-30

Phthalocyanines (Pcs) are commonly applied to advanced technologies such as optical limiting, photodynamic therapy (PDT), organic field-effect transistors (OFETs), and organic photovoltaic (OPV) devices, where they are used as the p-type layer. An approach to Pc structural diversity and the incorporation of a functional group that allows fabrication of solvent resistant Pc nanostructures formed by using a newly developed nanoimprint by melt processing (NIMP) technique, a variant of standard nanoimprint lithography (NIL), is reported. Copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), a click chemistry reaction, serves as an approach to structural diversity in Pc macrocycles. We have prepared octaalkynyl Pc 1b and have modified this Pc using the CuAAC reaction to yield four Pc derivatives 5a-5d with different peripheral substituents on the macrocycle. One of these derivatives, 5c, has photo-cross-linkable cinnamate residues, and we have demonstrated the fabrication of robust cross-linked photopatterned and imprinted nanostructures from this material.

Enhanced fluorescence of tetrasulfonated zinc phthalocyanine by graphene quantum dots and its application in molecular sensing/imaging.

PubMed

Wang, Jian; Zhang, Yanjun; Ye, Jiqing; Jiang, Zhou

2017-06-01

When excited at 435 nm, tetra-sulfonate zinc phthalocyanine (ZnPcS 4 ) emitted dual fluorescence at 495 and 702 nm. The abnormal fluorescence at 495 nm was experimentally studied and analyzed in detail for the first time. The abnormal fluorescence at 495 nm was deduced to originate from triplet-triplet (T-T) energy transfer of excited phthalocyanine ( 3 *ZnPcS 4 ). Furthermore, graphene quantum dots (GQDs) enhanced the 495 nm fluorescence quantum yield (Q) of ZnPcS 4 . The fluorescence properties of ZnPcS 4 -GQDs conjugate were retained in a cellular environment. Based on the fluorescence of ZnPcS 4 -GQDs conjugate, we designed and prepared an Apt29/thrombin/Apt15 sandwich thrombin sensor with high specificity and affinity. This cost-saving, simple operational sensing strategy can be extended to use in sensing/imaging of other biomolecules. Copyright © 2016 John Wiley & Sons, Ltd.

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films

PubMed Central

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J.; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G.; Headrick, Randall L.; McGill, Stephen A.; Furis, Madalina I.

2015-01-01

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ − d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of −4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials. PMID:26559337

Spin Exchange Interaction in Substituted Copper Phthalocyanine Crystalline Thin Films.

PubMed

Rawat, Naveen; Pan, Zhenwen; Lamarche, Cody J; Wetherby, Anthony; Waterman, Rory; Tokumoto, Takahisa; Cherian, Judy G; Headrick, Randall L; McGill, Stephen A; Furis, Madalina I

2015-11-12

The origins of spin exchange in crystalline thin films of Copper Octabutoxy Phthalocyanine (Cu-OBPc) are investigated using Magnetic Circular Dichroism (MCD) spectroscopy. These studies are made possible by a solution deposition technique which produces highly ordered films with macroscopic grain sizes suitable for optical studies. For temperatures lower than 2 K, the contribution of a specific state in the valence band manifold originating from the hybridized lone pair in nitrogen orbitals of the Phthalocyanine ring, bears the Brillouin-like signature of an exchange interaction with the localized d-shell Cu spins. A comprehensive MCD spectral analysis coupled with a molecular field model of a σπ - d exchange analogous to sp-d interactions in Diluted Magnetic Semiconductors (DMS) renders an enhanced Zeeman splitting and a modified g-factor of -4 for the electrons that mediate the interaction. These studies define an experimental tool for identifying electronic states involved in spin-dependent exchange interactions in organic materials.

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

PubMed Central

Gan, Patrick; Foord, John S; Compton, Richard G

2015-01-01

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur. PMID:26491640

Noncovalent binding of xanthene and phthalocyanine dyes with graphene sheets: the effect of the molecular structure revealed by a photophysical study.

PubMed

Zhang, Xian-Fu; Liu, Su-Ping; Shao, Xiao-Na

2013-09-01

The fluorescence and absorption properties of several xanthene and phthalocyanine dyes were measured in the presence and absence of chemically derived graphene (CDG) sheets. The interaction of pyronine Y (PYY) with graphene sheets was compared with that of rhodamine 6G (R6G) to reveal the effect of the molecular structure. Although the presence of the perpendicular benzene moiety in a R6G or phthalocyanine molecule does cause the difficulty for forming dye-CDG complex and make CDG less efficient in quenching the fluorescence intensity and shortening the fluorescence lifetime, it does not affect the band position of charge transfer absorption, suggesting that no molecular shape change occurred in a dye molecule caused by the interaction with CDG sheets. The spectroscopic and thermodynamic data indicated that the dye-CDG binding is of charge transfer nature, while the dynamic fluorescence quenching is due to photoinduced energy and electron transfer. Copyright © 2013 Elsevier B.V. All rights reserved.

Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures

PubMed Central

Zhang, Xing; Wu, Zishan; Zhang, Xiao; Li, Liewu; Li, Yanyan; Xu, Haomin; Li, Xiaoxiao; Yu, Xiaolu; Zhang, Zisheng; Liang, Yongye; Wang, Hailiang

2017-01-01

Electrochemical reduction of carbon dioxide with renewable energy is a sustainable way of producing carbon-neutral fuels. However, developing active, selective and stable electrocatalysts is challenging and entails material structure design and tailoring across a range of length scales. Here we report a cobalt-phthalocyanine-based high-performance carbon dioxide reduction electrocatalyst material developed with a combined nanoscale and molecular approach. On the nanoscale, cobalt phthalocyanine (CoPc) molecules are uniformly anchored on carbon nanotubes to afford substantially increased current density, improved selectivity for carbon monoxide, and enhanced durability. On the molecular level, the catalytic performance is further enhanced by introducing cyano groups to the CoPc molecule. The resulting hybrid catalyst exhibits >95% Faradaic efficiency for carbon monoxide production in a wide potential range and extraordinary catalytic activity with a current density of 15.0 mA cm−2 and a turnover frequency of 4.1 s−1 at the overpotential of 0.52 V in a near-neutral aqueous solution. PMID:28272403

Fluorination of Metal Phthalocyanines: Single-Crystal Growth, Efficient N-Channel Organic Field-Effect Transistors, and Structure-Property Relationships

PubMed Central

Jiang, Hui; Ye, Jun; Hu, Peng; Wei, Fengxia; Du, Kezhao; Wang, Ning; Ba, Te; Feng, Shuanglong; Kloc, Christian

2014-01-01

The fluorination of p-type metal phthalocyanines produces n-type semiconductors, allowing the design of organic electronic circuits that contain inexpensive heterojunctions made from chemically and thermally stable p- and n-type organic semiconductors. For the evaluation of close to intrinsic transport properties, high-quality centimeter-sized single crystals of F16CuPc, F16CoPc and F16ZnPc have been grown. New crystal structures of F16CuPc, F16CoPc and F16ZnPc have been determined. Organic single-crystal field-effect transistors have been fabricated to study the effects of the central metal atom on their charge transport properties. The F16ZnPc has the highest electron mobility (~1.1 cm2 V−1 s−1). Theoretical calculations indicate that the crystal structure and electronic structure of the central metal atom determine the transport properties of fluorinated metal phthalocyanines. PMID:25524460

Gold nanoparticle assemblies stabilized by bis(phthalocyaninato)lanthanide(III) complexes through van der Waals interactions

NASA Astrophysics Data System (ADS)

Noda, Yuki; Noro, Shin-Ichiro; Akutagawa, Tomoyuki; Nakamura, Takayoshi

2014-01-01

Gold nanoparticle assemblies possess diverse application potential, ranging from industrial nanotechnology to medical biotechnology. Because the structures and properties of assemblies are directly affected by the stabilization mechanism between the organic molecules serving as protecting ligands and the gold nanoparticle surface, it is crucial to find and investigate new stabilization mechanisms. Here, we report that π-conjugated phthalocyanine rings can serve as stabilizing ligands for gold nanoparticles. Bis(phthalocyaninato)lutetium(III) (LuPc2) or bis(phthalocyaninato)terbium(III) (TbPc2), even though complex, do not have specific binding units and stabilize gold nanoparticles through van der Waals interaction between parallel adsorbed phthalocyanine ligands and the gold nanoparticle surface. AC magnetic measurements and the electron-transport properties of the assemblies give direct evidence that the phthalocyanines are isolated from each other. Each nanoparticle shows weak electronic coupling despite the short internanoparticle distance (~1 nm), suggesting Efros-Shklovskii-type variable-range hopping and collective single-electron tunnelling behaviours.

Partial structural characterization and antioxidant activity of a phenolic-xylan from Castanea sativa hardwood.

PubMed

Renault, Emmanuel; Barbat-Rogeon, Aline; Chaleix, Vincent; Calliste, Claude-Alain; Colas, Cyril; Gloaguen, Vincent

2014-09-01

4-O-Methylglucuronoxylans (MGX) were isolated from chestnut wood sawdust using two different procedures: chlorite delignification followed by the classical alkaline extraction step, and an unusual green chemistry process of delignification using phthalocyanine/H2O2 followed by a simple extraction with hot water. Antioxidant properties of both MGX were evaluated against the stable radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) by electronic spin resonance (ESR). IC50 of water-extracted MGX was found to be less than 225 μg mL(-1), in contrast with alkali-extracted MGX for which no radical scavenging was observed. Characterization of extracts by colorimetric assay, GC, LC-MS and NMR spectroscopy provided some clues to understanding structure-function relationships of MGX in connection with their antioxidant activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Biological activities of phthalocyanines--XVI. Tetrahydroxy- and tetraalkylhydroxy zinc phthalocyanines. Effect of alkyl chain length on in vitro and in vivo photodynamic activities.

PubMed Central

Boyle, R. W.; Leznoff, C. C.; van Lier, J. E.

1993-01-01

Zinc phthalocyanine substituted with four hydroxyl groups attached to the macrocycle, either directly or via spacer chains of three or six carbon atoms, were tested for their photodynamic ability to inactivate Chinese hamster lung fibroblasts (line V-79) in vitro, and to induce regression of EMT-6 tumours grown subcutaneously in Balb/c mice. Their potential to inflict direct cell killing during photodynamic therapy was investigated by examining vascular stasis immediately following photoirradiation using fluorescein as a marker, and also by an in vivo/in vitro EMT-6 cell survival assay. Both of the tetraalkylhydroxy substituted zinc phthalocyanines are effective photodynamic sensitisers in vivo with the tetrapropylhydroxy compound exhibiting about twice the activity of the tetrahexylhydroxy analogue. The differences in activities were accentuated in vitro, the tetrapropylhydroxy compound was two orders of magnitude more potent than the tetrahexylhydroxy analogue in photoinactivating V-79 cells. The tetrahydroxy compound lacking spacer chains failed to exhibit photodynamic activity in either system. Tumour response with the active compounds was preceded by vascular stasis immediate following irradiation which suggests, together with the absence of activity in the in vivo/in vitro assay, that tumour regression involves an indirect response to the photodynamic action rather than direct cell killing. These data demonstrate the importance of the spatial orientation of functional groups around the macrocycle of photosensitisers for their efficacy in the photodynamic therapy of cancer. PMID:8512803

Enhanced activity and stability of binuclear iron (III) phthalocyanine on graphene nanosheets for electrocatalytic oxygen reduction in acid

NASA Astrophysics Data System (ADS)

Li, Tengfei; Peng, Yingxiang; Li, Kai; Zhang, Rui; Zheng, Lirong; Xia, Dingguo; Zuo, Xia

2015-10-01

Binuclear iron (III) phthalocyanine (bi-FePc) and iron (III) phthalocyanine (FePc) are synthesized in situ on graphene nanosheets (GNS) by a microwave-assisted method. TEM, ultraviolet-visible spectroscopy and Raman spectroscopy confirm that bi-FePc is supported on GNS through π-π interactions. The catalytic activity of the bi-FePc/GNS and FePc/GNS composites in the oxygen reduction reaction (ORR) is investigated by CV and RDE measurements. The bi-FePc/GNS composite shows a more positive onset potential (0.12 V vs. Hg/Hg2SO4) for the ORR than FePc/GNS (-0.02 V vs. Hg/Hg2SO4), and a four-electron mechanism similar to commercial Pt/C (0.22 V vs. Hg/Hg2SO4). Moreover, bi-FePc/GNS exhibits good stability with 100% retention after 36,000 s, while Pt/C has a retention of only 50% after the same period. Additionally, bi-FePc/GNS shows higher tolerance toward methanol than the Pt/C catalyst. XPS and X-ray absorption fine structure spectroscopy demonstrate that compared with FePc/GNS, bi-FePc/GNS possesses a higher concentration of Fe3+ and smaller skeleton radius of the phthalocyanine ring, which has a square-planar structure that evidently favors the ORR. Thus, bi-FePc/GNS is a promising candidate as a cathode catalyst in direct methanol fuel cells.

Enhancement of photodetection characteristics of MoS2 field effect transistors using surface treatment with copper phthalocyanine.

PubMed

Pak, Jinsu; Jang, Jingon; Cho, Kyungjune; Kim, Tae-Young; Kim, Jae-Keun; Song, Younggul; Hong, Woong-Ki; Min, Misook; Lee, Hyoyoung; Lee, Takhee

2015-11-28

Recently, two-dimensional materials such as molybdenum disulfide (MoS2) have been extensively studied as channel materials for field effect transistors (FETs) because MoS2 has outstanding electrical properties such as a low subthreshold swing value, a high on/off ratio, and good carrier mobility. In this study, we characterized the electrical and photo-responsive properties of MoS2 FET when stacking a p-type organic copper phthalocyanine (CuPc) layer on the MoS2 surface. We observed that the threshold voltage of MoS2 FET could be controlled by stacking the CuPc layers due to a charge transfer phenomenon at the interface. Particularly, we demonstrated that CuPc/MoS2 hybrid devices exhibited high performance as a photodetector compared with the pristine MoS2 FETs, caused by more electron-hole pairs separation at the p-n interface. Furthermore, we found the optimized CuPc thickness (∼2 nm) on the MoS2 surface for the best performance as a photodetector with a photoresponsivity of ∼1.98 A W(-1), a detectivity of ∼6.11 × 10(10) Jones, and an external quantum efficiency of ∼12.57%. Our study suggests that the MoS2 vertical hybrid structure with organic material can be promising as efficient photodetecting devices and optoelectronic circuits.

Synthesis, X-ray structure, magnetic resonance, and DFT analysis of a soluble copper(II) phthalocyanine lacking C-H bonds.

PubMed

Moons, Hans; Łapok, Łukasz; Loas, Andrei; Van Doorslaer, Sabine; Gorun, Sergiu M

2010-10-04

The synthesis, crystal structure, and electronic properties of perfluoro-isopropyl-substituted perfluorophthalocyanine bearing a copper atom in the central cavity (F(64)PcCu) are reported. While most halogenated phthalocyanines do not exhibit long-term order sufficient to form large single crystals, this is not the case for F(64)PcCu. Its crystal structure was determined by X-ray analysis and linked to the electronic properties determined by electron paramagnetic resonance (EPR). The findings are corroborated by density functional theory (DFT) computations, which agree well with the experiment. X-band continuous-wave EPR spectra of undiluted F(64)PcCu powder, indicate the existence of isolated metal centers. The electron-withdrawing effect of the perfluoroalkyl (R(f)) groups significantly enhances the complexes solubility in organic solvents like alcohols, including via their axial coordination. This coordination is confirmed by X-band (1)H HYSCORE experiments and is also seen in the solid state via the X-ray structure. Detailed X-band CW-EPR, X-band Davies and Mims ENDOR, and W-band electron spin-echo-detected EPR studies of F(64)PcCu in ethanol allow the determination of the principal g values and the hyperfine couplings of the metal, nitrogen, and fluorine nuclei. Comparison of the g and metal hyperfine values of F(64)PcCu and other PcCu complexes in different matrices reveals a dominant effect of the matrix on these EPR parameters, while variations in the ring substituents have only a secondary effect. The relatively strong axial coordination occurs despite the diminished covalency of the C-N bonds and potentially weakening Jahn-Teller effects. Surprisingly, natural abundance (13)C HYSCORE signals could be observed for a frozen ethanol solution of F(64)PcCu. The (13)C nuclei contributing to the HYSCORE spectra could be identified as the pyrrole carbons by means of DFT. Finally, (19)F ENDOR and easily observable paramagnetic NMR were found to relate well to the DFT computations, revealing negligible isotropic hyperfine (Fermi contact) contributions. The single-site isolation in solution and solid state and the relatively strong coordination of axial ligands, both attributed to the introduction of R(f) groups, are features important for materials and catalyst design.

Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling

DOE PAGES

Wagner, Sean R.; Feng, Jiagui; Yoon, Mina; ...

2015-08-25

Using scanning tunneling microscopy and density functional theory, we show that the molecular ordering and orientation of metal phthalocyanine molecules on the deactivated Si surface display a strong dependency on the central transition-metal ion, driven by the degree of orbital hybridization at the heterointerface via selective p – d orbital coupling. As a result, this Letter identifies a selective mechanism for modifying the molecule-substrate interaction which impacts the growth behavior of transition-metal-incorporated organic molecules on a technologically relevant substrate for silicon-based devices.

Direct measurements of nonlinear absorption and refraction in solutions of phthalocyanines

NASA Technical Reports Server (NTRS)

Wei, T. H.; Hagan, D. J.; Sence, M. J.; Van Stryland, E. W.; Perry, J. W.; Coulter, D. R.

1992-01-01

Direct measurements are reported of the excited singlet-state absorption cross section and the associated nonlinear refractive cross section using picosecond pulses at 532 nm in solutions of phthalocyanine and naphthalocyanine dyes. By monitoring the transmittance and far-field spatial beam distortion for different pulsewidths in the picosecond regime, it is shown that both the nonlinear absorption and refraction are fluence (energy-per-unit-area) rather than irradiance dependent. Thus, excited-state absorption is the dominant nonlinear absorption process, and the observed nonlinear refraction is also due to real population excitation.

Growth of copper phthalocyanine rods on Au plasmon electrodes through micelle disruption methods.

PubMed

Chen, Wei-Hung; Ko, Wen-Yin; Chen, Ying-Shiou; Cheng, Ching-Yuan; Chan, Chi-Ming; Lin, Kuan-Jiuh

2010-02-16

To improve the efficiency of the photocurrent conversion process, we have utilized copper phthalocyanine (CuPc) rods, which are capable of enhancing the interfacial area of electron transport and plasmonic gold nanoparticles (Au NPs), which can increase the separation and photogeneration of excitons, to produce a more effective system. In-plane horizontal CuPc rods, with diameters ranging from 0.2 to 1.5 microm, were electrodeposited onto the surface of plasmonic (Au NP) monolayers predeposited onto ITO substrates through electrolytic micelle disruption (EMD) methods.

Controlling the orbital sequence in individual Cu-phthalocyanine molecules.

PubMed

Uhlmann, C; Swart, I; Repp, J

2013-02-13

We report on the controlled change of the energetic ordering of molecular orbitals. Negatively charged copper(II)phthalocyanine on NaCl/Cu(100) undergoes a Jahn-Teller distortion that lifts the degeneracy of two frontier orbitals. The energetic order of the levels can be controlled by Au and Ag atoms in the vicinity of the molecule. As only one of the states is occupied, the control of the energetic order is accompanied by bistable changes of the charge distribution inside the molecule, rendering it a bistable switch.

Iron phthalocyanine modified mesoporous titania nanoparticles for photocatalytic activity and CO2 capture applications.

PubMed

Ramacharyulu, P V R K; Muhammad, Raeesh; Praveen Kumar, J; Prasad, G K; Mohanty, Paritosh

2015-10-21

An iron(II)phthalocyanine (Fepc) modified mesoporous titania (Fepc-TiO2) nanocatalyst with a specific surface area of 215 m(2) g(-1) has been synthesized by a hydrothermal method. Fepc-TiO2 degrades one of the highly toxic chemical warfare agents, sulfur mustard (SM), photocatalytically under sunlight with an exposure time of as low as 70 min. Furthermore, the mesoporous Fepc-TiO2 also captured 2.1 mmol g(-1) of CO2 at 273 K and 1 atm.

A multi-analytical approach for the characterization of wall painting materials on contemporary buildings

NASA Astrophysics Data System (ADS)

Magrini, Donata; Bracci, Susanna; Cantisani, Emma; Conti, Claudia; Rava, Antonio; Sansonetti, Antonio; Shank, Will; Colombini, MariaPerla

2017-02-01

Samples from Keith Haring's wall painting of the Necker Children Hospital in Paris were studied by a multi-analytical protocol. X-ray fluorescence (XRF), powder X-ray diffraction (XRDP), Electron microscope (SEM-EDS), Infrared and Raman spectroscopy (μ-FT-IR and μ-Raman) measurements were performed in order to characterize the materials and to identify the art technique used to produce this contemporary work. Materials from the mural suffered from severe detachments of materials and several fragments were found on the ground beneath. Some of these fragments, which were representative of the whole palette and stratigraphic sequence, were collected and studied. The fragments were sufficiently large to enable non-invasive measurements to be performed in order to characterize the materials. A comparison of the data of the techniques applied revealed that Haring's palette was composed of organic pigments such as Naphtol red, phthalocyanine blue and green and Hansa yellow, in accordance with those used previously by the artist in other painted murals.

Direct synthesis of nitrogen-containing carbon nanotubes on carbon paper for fuel cell electrode

NASA Astrophysics Data System (ADS)

Yin, Wong Wai; Daud, Wan Ramli Wan; Mohamad, Abu Bakar; Kadhum, Abdul Amir Hassan; Majlan, Edy Herianto; Shyuan, Loh Kee

2012-06-01

Organic catalyst has recently been identified as the potential substitution for expensive platinum electrocatalyst for fuel cell application. Numerous studies have shown that the nitrogen-containing carbon nanotubes (N-CNT) can be synthesized through spray pyrolysis or floating chemical vapor deposition (CVD) technique using various type of organometallic as precursors. This paper presents the method of synthesis and the initial findings of the growth of N-CNT directly on carbon paper using a modified CVD technique. In this research, nickel (II) phthalocyanines (Ni-Pc) as precursor was dissolved in ethanol solvent, stirred and sonicated to become homogenized. The solution was poured into a bubbler and heated up to allow the mixture to vaporize. Subsequently, the solution vapor was flowed into the tubical reactor maintained at 900°C. Carbon paper sputtered with nickel nanoparticles was used as the substrate. The synthesized sample was examined through Field Emission Scanning Electron Microscopy (FESEM), Atomic Force Microscopy (AFM) and Fourier Transform Infra-Red (FTIR). Long, entangled and compartmentalized nanotubes with tube diameter ranging 23-27 nm were found covered the carbon paper surface with approximate of 5.5-6.0 μm in thickness. EDX analysis has successfully showed the presence of nitrogen in the carbon nanotube. FTIR analysis showed the presence of the C-N bond on CNT.

Bis(tri-n-hexylsilyl oxide) silicon phthalocyanine: a unique additive in ternary bulk heterojunction organic photovoltaic devices.

PubMed

Lessard, Benoît H; Dang, Jeremy D; Grant, Trevor M; Gao, Dong; Seferos, Dwight S; Bender, Timothy P

2014-09-10

Previous studies have shown that the use of bis(tri-n-hexylsilyl oxide) silicon phthalocyanine ((3HS)2-SiPc) as an additive in a P3HT:PC61BM cascade ternary bulk heterojunction organic photovoltaic (BHJ OPV) device results in an increase in the short circuit current (J(SC)) and efficiency (η(eff)) of up to 25% and 20%, respectively. The previous studies have attributed the increase in performance to the presence of (3HS)2-SiPc at the BHJ interface. In this study, we explored the molecular characteristics of (3HS)2-SiPc which makes it so effective in increasing the OPV device J(SC) and η(eff. Initially, we synthesized phthalocyanine-based additives using different core elements such as germanium and boron instead of silicon, each having similar frontier orbital energies compared to (3HS)2-SiPc and tested their effect on BHJ OPV device performance. We observed that addition of bis(tri-n-hexylsilyl oxide) germanium phthalocyanine ((3HS)2-GePc) or tri-n-hexylsilyl oxide boron subphthalocyanine (3HS-BsubPc) resulted in a nonstatistically significant increase in JSC and η(eff). Secondly, we kept the silicon phthalocyanine core and substituted the tri-n-hexylsilyl solubilizing groups with pentadecyl phenoxy groups and tested the resulting dye in a BHJ OPV. While an increase in JSC and η(eff) was observed at low (PDP)2-SiPc loadings, the increase was not as significant as (3HS)2-SiPc; therefore, (3HS)2-SiPc is a unique additive. During our study, we observed that (3HS)2-SiPc had an extraordinary tendency to crystallize compared to the other compounds in this study and our general experience. On the basis of this observation, we have offered a hypothesis that when (3HS)2-SiPc migrates to the P3HT:PC61BM interface the reason for its unique performance is not solely due to its frontier orbital energies but also might be due to a high driving force for crystallization.

Assessing the potential of group 13 and 14 metal/metalloid phthalocyanines as hole transport layers in organic light emitting diodes

NASA Astrophysics Data System (ADS)

Plint, Trevor; Lessard, Benoît H.; Bender, Timothy P.

2016-04-01

In this study, we have assessed the potential application of group 13 and 14 metal and metalloid phthalocyanines ((X)n-MPcs) and their axially substituted derivatives as hole-transporting layers in organic light emitting diodes (OLEDs). OLEDs studied herein have the generic structure of glass/ITO/(N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB) or (X)n-MPc)(50 nm)/Alq3 (60 nm)/LiF (1 nm)/Al (80 nm), where X is an axial substituent group. OLEDs using chloro aluminum phthalocyanine (Cl-AlPc) showed good peak luminance values of 2620 ± 113 cd/m2 at 11 V. To our knowledge, Cl-AlPc has not previously been shown to work as a hole transport material (HTL) in OLEDs. Conversely, the di-chlorides of silicon, germanium, and tin phthalocyanine (Cl2-SiPc, Cl2-GePc, and Cl2-SnPc, respectively) showed poor performance compared to Cl-AlPc, having peak luminances of only 38 ± 4 cd/m2 (12 V), 23 ± 1 cd/m2 (8.5 V), and 59 ± 5 cd/m2 (13.5 V), respectively. However, by performing a simple axial substitution of the chloride groups of Cl2-SiPc with pentafluorophenoxy groups, the resulting bis(pentafluorophenoxy) silicon phthalocyanine (F10-SiPc) containing OLED had a peak luminance of 5141 ± 941 cd/m2 (10 V), a two order of magnitude increase over its chlorinated precursor. This material showed OLED characteristics approaching those of a baseline OLED based on the well-studied triarylamine NPB. Attempts to attach the pentafluorophenoxy axial group to both SnPc and GePc were hindered by synthetic difficulties and low thermal stability, respectively. In light of the performance improvements observed by simple axial substitution of SiPc in OLEDs, the use of axially substituted MPcs in organic electronic devices remains of continuing interest to us and potentially the field in general.

Regioregular Phthalocyanines Substituted with Bulky Donors at Non-Peripheral Positions.

PubMed

Yamamoto, Satoshi; Kuribayashi, Kengo; Murakami, Takuro N; Kwon, Eunsang; Stillman, Martin J; Kobayashi, Nagao; Segawa, Hiroshi; Kimura, Mutsumi

2017-11-02

Three regioregular phthalocyanines (1-3) were synthesized selectively by the cyclic tetramerization of phthalonitriles bearing a bulky diarylamine substituent at the next position of nitrile. The steric repulsion at the tetramerization of bulky phthalonitriles allowed for the selective formation of regioregular phthalocyanines as confirmed by NMR and single crystal X-ray structural analyses. The absorption spectrum of 1 substituted with di(4-tert-butylphenyl)amine groups at the non-peripheral positions showed a non-split Q-band at 764 nm, which was redshifted by 83 nm compared with that of metal free phthalocyanine (H 2 Pc). The TD-DFT calculation and electrochemical studies prove that the substitution of diarylamine groups at the α-positions effectively destabilizes the HOMO energy level, which causes a large redshift of the Q-band. Moreover, 1 can generate a one-electron oxidation species through chemical oxidation. The Q-band position of 2 bearing 4,4'-dimetoxyphenylamine units was further shifted by 10 nm compared with that of 1. In addition, 3 having carbazole units showed a small redshift of the Q-band relative to H 2 Pc. The hole-mobility of 2 in thin film was determined to be 1.1×10 -5  cm V -1  s -1 by using a space charge limited current method. A perovskite solar cell employing 2 as a hole-transporting layer gave an efficiency of 5.1 % under standard global 100 Wcm -2 AM 1.5 G illumination. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An ab-initio density functional theory investigation of fullerene/Zn-phthalocyanine (C60/ZnPc) interface with face-on orientation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Javaid, Saqib; National Centre of Physics, Islamabad; Javed Akhtar, M., E-mail: javedakhtar6@gmail.com

2015-07-28

We have employed density functional theory to study the C60/ZnPc interface with face-on orientation, which has recently been tailored experimentally. For this purpose, adsorption of ZnPc on C60 has been studied, while taking into account different orientations of C60. Out of various adsorption sites investigated, 6:6 C-C bridge position in apex configuration of C60 has been found energetically the most favourable one with C60-ZnPc adsorption distance of ∼2.77 Å. The adsorption of ZnPc on C60 ensues both charge re-organization and charge transfer at the interface, resulting in the formation of interface dipole. Moreover, by comparing results with that of C60/CuPc interface,more » we show that the direction of interface dipole can be tuned by the change of the central atom of the phthalocyanine molecule. These results highlight the complexity of electronic interactions present at the C60/Phthalocyanine interface.« less

Frenkel-Charge-Transfer exciton intermixing theory for molecular crystals with two isolated Frenkel exciton states.

NASA Astrophysics Data System (ADS)

Bondarev, Igor; Popescu, Adrian

We develop an analytical theory for the intra-intermolecular exciton intermixing in periodic 1D chains of planar organic molecules with two isolated low-lying Frenkel exciton states, typical of copper phthalocyanine (CuPc) and other transition metal phthalocyanine molecules. We formulate the Hamiltonian and use the exact Bogoliubov diagonalization procedure to derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer (CT) exciton state. By comparing our theoretical spectrum with available experimental CuPc absorption data, we obtain the parameters of the Frenkel-CT exciton intermixing in CuPc thin films. The two Frenkel exciton states here are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the CT exciton, showing the coupling constant 0.17 eV in agreement with earlier electron transport experiments. Our results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines. DOE-DE-SC0007117 (I.B.), UNC-GA ROI Grant (A.P.).

Polyoxometalate-modified TiO2 nanotube arrays photoanode materials for enhanced dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Liu, Ran; Sun, Zhixia; Zhang, Yuzhuo; Xu, Lin; Li, Na

2017-10-01

In this work, we prepared for the first time the TiO2 nanotube arrays (TNAs) photoanode with polyoxometalate(POMs)-modified TiO2 electron-transport layer for improving the performance of zinc phthalocyanine(ZnPc)-sensitized solar cells. The as-prepared POMs/TNAs/ZnPc composite photoanode exhibited higher photovoltaic performances than the TNAs/ZnPc photoanode, so that the power conversion efficiency of the solar cell device based on the POMs/TNAs/ZnPc photoanode displayed a notable improvement of 45%. These results indicated that the POMs play a key role in reducing charge recombination in phthalocyanine-sensitized solar cells, together with TiO2 nanotube arrays being helpful for electron transport. The mechanism of the performance improvement was demonstrated by the measurements of electrochemical impedance spectra and open-circuit voltage decay curves. Although the resulting performance is still below that of the state-of-the-art dye-sensitized solar cells, this study presents a new insight into improving the power conversion efficiency of phthalocyanine-sensitized solar cells via polyoxometalate-modified TiO2 nanotube arrays photoanode.

In-situ spectro-microscopy on organic films: Mn-Phthalocyanine on Ag(100)

NASA Astrophysics Data System (ADS)

Al-Mahboob, Abdullah; Sadowski, Jerzy T.; Vescovo, Elio

2013-03-01

Metal phthalocyanines are attracting significant attention, owing to their potential for applications in chemical sensors, solar cells and organic magnets. As the electronic properties of molecular films are determined by their crystallinity and molecular packing, the optimization of film quality is important for improving the performance of organic devices. Here, we present the results of in situ low-energy electron microscopy / photoemission electron microscopy (LEEM/PEEM) studies of incorporation-limited growth of manganese-phthalocyanine (MnPc) on Ag(100) surfaces. MnPc thin films were grown on both, bulk Ag(100) surface and thin Ag(100)/Fe(100) films, where substrate spin-polarized electronic states can be modified through tuning the thickness of the Ag film. We also discuss the electronic structure and magnetic ordering in MnPc thin films, investigated by angle- and spin-resolved photoemission spectroscopy. Research carried out at the Center for Functional Nanomaterials and National Synchrotron Light Source, Brookhaven National Laboratory, which are supported by the U.S. Dept. of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.

Azaphenalene phthalocyanines: phthalocyanine analogues with six-membered-ring units instead of five-membered-ring units.

PubMed

Shimizu, Soji; Zhu, Hua; Kobayashi, Nagao

2010-09-24

Mixed-condensation reaction of 1,8-naphthalenedicarbonitrile and a 4,5-disubstituted phthalonitrile provided a series of phthalocyanine (Pc) analogues with azaphenalene (AP) moieties in place of the isoindole moieties. Monosubstituted species, APPc, and the two structural isomers of disubstituted species, adj-AP(2)Pc and opp-AP(2)Pc, were successfully isolated by gel-permeation chromatography on HPLC apparatus. Their structures were elucidated by (1)H NMR spectroscopy and X-ray crystallographic analysis. Replacement of the isoindole moieties with azaphenalene moieties created six-membered-ring units in the core and caused distortion of the molecular structures. The Q-band absorption shifted to the red upon an increase in the number of azaphenalene units; the shape of the absorption spectra depended on the molecular symmetries. APPc and opp-AP(2)Pc showed a large splitting of the Q band, whereas adj-AP(2)Pc exhibited a single broad Q band. These changes in the absorption spectra, as well as the unique electronic structures, are discussed in detail, based on magnetic circular dichroism spectra, electrochemical measurements, and density functional theory calculations.

Photophysicochemical properties and photodynamic therapy activity of highly water-soluble Zn(II) phthalocyanines.

PubMed

Oluwole, David O; Sarı, Fatma Aslıhan; Prinsloo, Earl; Dube, Edith; Yuzer, Abdulcelil; Nyokong, Tebello; Ince, Mine

2018-05-29

The syntheses of two zinc(II) phthalocyanines (ZnPcs) having either imidazole (ZnPc 1) or pyridiloxy (ZnPc 2) moieties as their macrocycle substituents are reported. Quaternization of the ZnPcs with methyl iodide afforded water soluble cationic phthalocyanines. The photophysical, photochemical properties and photodynamic therapy (PDT) activity of the ZnPcs were studied in solution. The fluorescence quantum yield and lifetime of ZnPc 1 were higher as compared to ZnPc 2. ZnPc 2 afforded higher triplet state (Φ T ) and singlet oxygen quantum yields (Φ Δ ) in comparison to ZnPc 1. The PDT activity of ZnPcs was investigated against human breast adenocarcinoma cells (MCF-7). The two compounds afforded a very minimal in vitro dark cytotoxicity with 85% viable cells at concentration ≤80 μM. On irradiation of the cells having the ZnPcs, ≥50% cell death was recorded for ZnPc 1 which was also evidenced by the cells photo-micrograph. Copyright © 2018 Elsevier B.V. All rights reserved.

Ultrafast Charge Transfer in Nickel Phthalocyanine Probed by Femtosecond Raman-Induced Kerr Effect Spectroscopy

PubMed Central

2015-01-01

The recently developed technique of femtosecond stimulated Raman spectroscopy, and its variant, femtosecond Raman-induced Kerr effect spectroscopy (FRIKES), offer access to ultrafast excited-state dynamics via structurally specific vibrational spectra. We have used FRIKES to study the photoexcitation dynamics of nickel(II) phthalocyanine with eight butoxy substituents, NiPc(OBu)8. NiPc(OBu)8 is reported to have a relatively long-lived ligand-to-metal charge-transfer (LMCT) state, an essential characteristic for efficient electron transfer in photocatalysis. Following photoexcitation, vibrational transitions in the FRIKES spectra, assignable to phthalocyanine ring modes, evolve on the femtosecond to picosecond time scales. Correlation of ring core size with the frequency of the ν10 (asymmetric C–N stretching) mode confirms the identity of the LMCT state, which has a ∼500 ps lifetime, as well as that of a precursor d-d excited state. An even earlier (∼0.2 ps) transient is observed and tentatively assigned to a higher-lying Jahn–Teller-active LMCT state. This study illustrates the power of FRIKES spectroscopy in elucidating ultrafast molecular dynamics. PMID:24841906

The water soluble peripherally tetra-substituted zinc(ii), manganese(iii) and copper(ii) phthalocyanines as new potential anticancer agents.

PubMed

Barut, Burak; Sofuoğlu, Ayşenur; Biyiklioglu, Zekeriya; Özel, Arzu

2016-09-28

In this study, [2-(2-morpholin-4-ylethoxy)ethoxy] group substituted zinc(ii), manganese(iii) and copper(ii) phthalocyanines 2-4 and their water soluble derivatives 2a, 3a and 4a were synthesized and the interactions of compounds 2a, 3a and 4a with CT-DNA and supercoiled pBR322 plasmid DNA were investigated. The results of binding experiments showed that these compounds were able to interact with CT-DNA via intercalative mode with a strong binding affinity in the order 3a > 2a > 4a. DNA-photocleavage activities of compounds 2a, 3a and 4a were determined. These compounds cleaved supercoiled pBR322 plasmid DNA efficiently under irradiation at 650 nm for 2a and 4a, and at 750 nm for 3a. These compounds displayed remarkable inhibitory activities against topoisomerase I enzyme in a dose-dependent manner. All of these results suggest that these phthalocyanines might be suitable anticancer agents due to their strong binding affinities, significant cleavage activities and effective topoisomerase I inhibition.

A zinc phthalocyanine based periodic mesoporous organosilica exhibiting charge transfer to fullerenes.

PubMed

Auras, Florian; Li, Yan; Löbermann, Florian; Döblinger, Markus; Schuster, Jörg; Peter, Laurence M; Trauner, Dirk; Bein, Thomas

2014-11-10

Periodic mesoporous organosilica (PMO) materials offer a strategy to position molecular semiconductors within a highly defined, porous network. We developed thin films of a new semiconducting zinc phthalocyanine-bridged PMO exhibiting a face-centered orthorhombic pore structure with an average pore diameter of 11 nm. The exceptional degree of order achieved with this PMO enabled us to create thin films consisting of a single porous domain throughout their entire thickness, thus providing maximal accessibility for subsequent incorporation of a complementary phase. The phthalocyanine building blocks inside the pore walls were found to be well-aggregated, enabling electronic conductivity and extending the light-harvesting capabilities to the near IR region. Ordered 3D heterojunctions capable of promoting photo-induced charge transfer were constructed by impregnation of the PMO with a fullerene derivative. When integrated into a photovoltaic device, the infiltrated PMO is capable of producing a high open-circuit voltage and a considerable photocurrent, which represents a significant step towards potential applications of PMOs in optoelectronics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of temperature on series resistance of organic/inorganic semiconductor junction diode

NASA Astrophysics Data System (ADS)

Tripathi, Udbhav; Kaur, Ramneek; Bharti, Shivani

2016-05-01

The paper reports the fabrication and characterization of CuPc/n-Si organic/inorganic semiconductor diode. Copper phthalocyanine, a p-type organic semiconductor layer has been deposited on Si substrate by thermal evaporation technique. The detailed analysis of the forward and reverse bias current-voltage characteristics has been provided. Temperature dependence of the schottky diode parameters has been studied and discussed in the temperature range, 303 K to 353 K. Series resistance of the diode has been determined using Cheung's function method. Series resistance decreases with increase in temperature. The large value of series resistance at low temperature has been explained on the basis of barrier inhomogeneities in the diode.

Spacecraft dielectric material properties and spacecraft charging

NASA Technical Reports Server (NTRS)

Frederickson, A. R.; Wall, J. A.; Cotts, D. B.; Bouquet, F. L.

1986-01-01

The physics of spacecraft charging is reviewed, and criteria for selecting and testing semiinsulating polymers (SIPs) to avoid charging are discussed and illustrated. Chapters are devoted to the required properties of dielectric materials, the charging process, discharge-pulse phenomena, design for minimum pulse size, design to prevent pulses, conduction in polymers, evaluation of SIPs that might prevent spacecraft charging, and the general response of dielectrics to space radiation. SIPs characterized include polyimides, fluorocarbons, thermoplastic polyesters, poly(alkanes), vinyl polymers and acrylates, polymers containing phthalocyanine, polyacene quinones, coordination polymers containing metal ions, conjugated-backbone polymers, and 'metallic' conducting polymers. Tables summarizing the results of SIP radiation tests (such as those performed for the NASA Galileo Project) are included.

Performance of (CoPC)n catalyst in active lithium-thionyl chloride cells

NASA Technical Reports Server (NTRS)

Shah, Pinakin M.

1990-01-01

An experimental study was conducted with anode limited D size cells to characterize the performance of an active lithium-thionyl chloride (Li/SOCl2) system using the polymeric cobalt phthalocyanine, (CoPC)n, catalyst in carbon cathodes. The author describes the results of this experiment with respect to initial voltage delays, operating voltages, and capacities. The effectiveness of the preconditioning methods evolved to alleviate passivation effects on storage are also discussed. The results clearly demonstrated the superior high rate capability of cells with the catalyst. The catalyst did not adversely impact the performance of cells after active storage for up to 6 months, while retaining its beneficial influences.

Dendritic copper phthalocyanine with aggregation induced blue emission and solid-state fluorescence

NASA Astrophysics Data System (ADS)

Wang, Jiayi; Pan, Lin; Zhou, Xuefei; Jia, Kun; Liu, Xiaobo

2016-09-01

In this work, dendritic copper phthalocyanine (CuPc) showing obvious aggregation induced emission (AIE) and strong solid-state fluorescence was synthesized. It was found that synthesized CuPc can be easily solubilized in polar aprotic solvent, where no fluorescence signal was detected. Interestingly, both the CuPc aggregates in solution and solid-state powder exhibited strong fluorescence emission around 480 nm, which should be attributed to the restriction of intramolecular rotation as rationalized in aggregation induced emission framework. Meanwhile the obvious crystalline enhanced solid-state fluorescent emission is observed for CuPc powder.

Apoptosis of mouse MS-2 fibrosarcoma cells induced by photodynamic therapy with Zn (II)-phthalocyanine.

PubMed

Zhou, C; Shunji, C; Jinsheng, D; Junlin, L; Jori, G; Milanesi, C

1996-05-01

The destructive process of mouse MS-2 fibrosarcoma induced by photodynamic therapy (PDT) with liposome-administered Zn(II)-phthalocyanine (ZnPc) was studied by electron microscopy. Pronounced ultrastructural changes characteristic of apoptosis were observed for several tumour cells, including early occurrence of condensation and margination of chromatin, disappearance of nuclear pores, karyopyknosis, karyorrhexis, protuberance formation at the cell surface and cell fragmentation. The findings indicate that apoptosis was involved in the process of tumour cell death induced by ZnPc-PDT. The detailed mechanism and pathways controlling this phenomenon need to be elucidated further.

Microsolvation of phthalocyanine molecules in superfluid helium nanodroplets as revealed by the optical line shape at electronic origin.

PubMed

Fuchs, S; Fischer, J; Slenczka, A; Karra, M; Friedrich, B

2018-04-14

We investigate the solvent shift of phthalocyanine (Pc) doped into superfluid helium droplets and probed by optical spectroscopy at the electronic origin. Our present work complements extant studies and provides results that in part contradict previous conclusions. In particular, the solvent shift does not increase monotonously with droplet radius all the way up to the bulk limit, but exhibits just the reverse dependence instead. Moreover, a substructure is resolved, whose characteristics depend on the droplet size. This behavior can hardly be reconciled with that of a freely rotating Pc-helium complex.

Photophysics of the geminate polaron-pair state in copper phthalocyanine organic photovoltaic blends: evidence for enhanced intersystem crossing.

PubMed

Snedden, Edward W; Monkman, Andrew P; Dias, Fernando B

2013-04-04

Geminate polaron-pair recombination directly to the triplet state of the small dye molecule copper(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H- phthalocyanine (CuPC) and exciton trapping in CuPC domains, combine to reduce the internal quantum efficiency of free polaron formation in the bulk-heterojunction blends of CuPC doped with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as the electron acceptor. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The electronic properties of potassium doped copper-phthalocyanine studied by electron energy-loss spectroscopy.

PubMed

Flatz, K; Grobosch, M; Knupfer, M

2007-06-07

The authors have studied the electronic structure of potassium doped copper-phthalocyanine using electron energy-loss spectroscopy. The evolution of the loss function indicates the formation of distinct KxCuPc phases. Taking into account the C1s and K2p core level excitations and recent results by Giovanelli et al. [J. Chem. Phys. 126, 044709 (2007)], they conclude that these are K2CuPc and K4CuPc. They discuss the changes in the electronic excitations upon doping on the basis of the molecular electronic levels and the presence of electronic correlations.

Defect states and their energetic position and distribution in organic molecular semiconductors

NASA Astrophysics Data System (ADS)

Sharma, Akanksha; Yadav, Sarita; Kumar, Pramod; Ray Chaudhuri, Sumita; Ghosh, Subhasis

2013-04-01

Energetic position and distribution of defect states due to structural disorder in pentacene and copper phthalocyanine have been obtained by capacitance based spectroscopic techniques. It has been shown that capacitance-frequency and capacitance-voltage characteristics exhibit Gaussian distribution of traps with an energetic position at around 0.5 eV above the highest occupied molecular orbital level of the pentacene and CuPc. These traps have been created by varying growth conditions and almost identical trap parameters in pentacene and copper phthalocyanine indicate that similar structural disorder is responsible for these traps.

Superstructures and Electronic Properties of Manganese-Phthalocyanine Molecules on Au(110) from Submonolayer Coverage to Ultrathin Molecular Films.

PubMed

Topyła, M; Néel, N; Kröger, J

2016-07-12

The adsorption of manganese-phthalocyanine molecules on Au(110) was investigated using a low-temperature scanning tunneling microscope. A rich variety of commensurate superstructures was observed upon increasing the molecule coverage from submonolayers to ultrathin films. All structures were associated with reconstructions of the Au(110) substrate. Molecules adsorbed in the second molecular layer exhibited negative differential conductance occurring symmetrically around zero bias voltage. A double-barrier tunneling model rationalized this observation in terms of a peaked molecular resonance at the Fermi energy together with a voltage drop across the molecular film.

Rhenium-phthalocyanine molecular nanojunction with high magnetic anisotropy and high spin filtering efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, J.; Institute of Nanomaterial and Nanostructure, Changsha University of Science and Technology, Changsha 410114; Hu, J.

2015-07-20

Using the density functional and non-equilibrium Green's function approaches, we studied the magnetic anisotropy and spin-filtering properties of various transition metal-Phthalocyanine molecular junctions across two Au electrodes. Our important finding is that the Au-RePc-Au junction has both large spin filtering efficiency (>80%) and large magnetic anisotropy energy, which makes it suitable for device applications. To provide insights for the further experimental work, we discussed the correlation between the transport property, magnetic anisotropy, and wave function features of the RePc molecule, and we also illustrated the possibility of controlling its magnetic state.

Oligo p-Phenylenevinylene Derivatives as Electron Transfer Matrices for UV-MALDI

NASA Astrophysics Data System (ADS)

Castellanos-García, Laura J.; Agudelo, Brian Castro; Rosales, Hernando F.; Cely, Melissa; Ochoa-Puentes, Christian; Blanco-Tirado, Cristian; Sierra, Cesar A.; Combariza, Marianny Y.

2017-12-01

Phenylenevinylene oligomers (PVs) have outstanding photophysical characteristics for applications in the growing field of organic electronics. Yet, PVs are also versatile molecules, the optical and physicochemical properties of which can be tuned by manipulation of their structure. We report the synthesis, photophysical, and MS characterization of eight PV derivatives with potential value as electron transfer (ET) matrices for UV-MALDI. UV-vis analysis show the presence of strong characteristic absorption bands in the UV region and molar absorptivities at 355 nm similar or higher than those of traditional proton (CHCA) and ET (DCTB) MALDI matrices. Most of the PVs exhibit non-radiative quantum yields (φ) above 0.5, indicating favorable thermal decay. Ionization potential values (IP) for PVs, calculated by the Electron Propagator Theory (EPT), range from 6.88 to 7.96 eV, making these oligomers good candidates as matrices for ET ionization. LDI analysis of PVs shows only the presence of radical cations (M+.) in positive ion mode and absence of clusters, adducts, or protonated species; in addition, M+. threshold energies for PVs are lower than for DCTB. We also tested the performance of four selected PVs as ET MALDI matrices for analytes ranging from porphyrins and phthalocyanines to polyaromatic compounds. Two of the four PVs show S/N enhancement of 1961% to 304% in comparison to LDI, and laser energy thresholds from 0.17 μJ to 0.47 μJ compared to 0.58 μJ for DCTB. The use of PV matrices also results in lower LODs (low fmol range) whereas LDI LODs range from pmol to nmol. [Figure not available: see fulltext.

Nanoparticle Additives for Multiphase Systems: Synthesis, Formulation and Characterization

DTIC Science & Technology

2012-01-01

ADDITIVES FOR MULTIPHASE SYSTEMS: SYNTHESIS , FORMULATION AND CHARACTERIZATION Vinod Kanniah University of Kentucky, vinodkanniah@gmail.com This Doctoral...UKnowledge@lsv.uky.edu. Recommended Citation Kanniah, Vinod, "NANOPARTICLE ADDITIVES FOR MULTIPHASE SYSTEMS: SYNTHESIS , FORMULATION AND CHARACTERIZATION...00-00-2012 to 00-00-2012 4. TITLE AND SUBTITLE Nanoparticle Additives for Multiphase Systems: Synthesis , Formulation and Characterization 5a

Phase modification of copper phthalocyanine semiconductor by converting powder to thin film

NASA Astrophysics Data System (ADS)

Ai, Xiaowei; Lin, Jiaxin; Chang, Yufang; Zhou, Lianqun; Zhang, Xianmin; Qin, Gaowu

2018-01-01

Thin films of copper phthalocyanine (CuPc) semiconductor were deposited on glass substrates by a thermal evaporation system using the CuPc powder in a high vacuum. The crystal structures of both the films and the powder were measured by the X-ray diffraction spectroscopy technique. It is observed that CuPc films only show one peak at 6.84°, indicating a high texture of α phase along (200) orientation. In comparison, CuPc powder shows a series of peaks, which are confirmed from the mixture of both α and β phases. The effects of substrate anneal temperature on the film structure, grain size and optical absorption property of CuPc films were also investigated. All the films are of α phase and the full width of half maximum for (200) diffraction peak becomes narrow with increasing the substrate temperatures. The average grain size calculated by the Scherrer's formula is 33.63 nm for the film without anneal, which is increased up to 58.29 nm for the film annealed at 200 °C. Scanning electron microscope was further measured to prove the growth of crystalline grain and to characterize the morphologies of CuPc films. Ultraviolet-visible absorption spectra were employed to study the structure effect on the optical properties of both CuPc films and powder. Fourier Transform infrared spectroscopy was used to identify the crystalline nature of both CuPc powder and film.

Electrochemical Sensors Based on Screen-Printed Electrodes: The Use of Phthalocyanine Derivatives for Application in VFA Detection

PubMed Central

Ndiaye, Amadou L.; Delile, Sébastien; Brunet, Jérôme; Varenne, Christelle; Pauly, Alain

2016-01-01

Here, we report on the use of electrochemical methods for the detection of volatiles fatty acids (VFAs), namely acetic acid. We used tetra-tert-butyl phthalocyanine (PcH2-tBu) as the sensing material and investigated its electroanalytical properties by means of cyclic voltammetry (CV) and square wave voltammetry (SWV). To realize the electrochemical sensing system, the PcH2-tBu has been dropcast-deposited on carbon (C) orgold (Au)screen-printed electrodes (SPEs) and characterized by cyclic voltammetry and scanning electron microscopy (SEM). The SEM analysis reveals that the PcH2-tBu forms mainly aggregates on the SPEs. The modified electrodes are used for the detection of acetic acid and present a linear current increase when the acetic acid concentration increases. The Cmodified electrode presents a limit of detection (LOD) of 25.77 mM in the range of 100 mM–400 mM, while the Aumodified electrode presents an LOD averaging 40.89 mM in the range of 50 mM–300 mM. When the experiment is realized in a buffered condition, theCmodified electrode presents a lower LOD, which averagesthe 7.76 mM. A pronounced signal decay attributed to an electrode alteration is observed in the case of the gold electrode. This electrode alteration severely affects the coating stability. This alteration is less perceptible in the case of the carbon electrode. PMID:27598214

Evaluation of photodynamic activity, photostability and in vitro drug release of zinc phthalocyanine-loaded nanocapsules.

PubMed

de Souza, Thiane Deprá; Ziembowicz, Francieli Isa; Müller, Debora Friedrich; Lauermann, Sâmera Cristina; Kloster, Carmen Luisa; Santos, Roberto Christ Vianna; Lopes, Leonardo Quintana Soares; Ourique, Aline Ferreira; Machado, Giovanna; Villetti, Marcos Antonio

2016-02-15

Nanocapsule formulations containing zinc phthalocyanine (ZnPc) were investigated as drug delivery systems for use in photodynamic therapy (PDT). ZnPc loaded chitosan, PCL, and PCL coated with chitosan nanocapsules were prepared and characterized by means of their physicochemical properties, photodynamic activity, photostability and drug release profile. All formulations presented nanometric hydrodynamic radius, around 100 nm, low polydispersity index (0.08-0.24), slightly negative zeta potential for PCL nanoparticles and positive zeta potential for suspension containing chitosan. Encapsulation efficiencies were higher than 99%. The capacity of ZnPc loaded nanocapsules to produce cytotoxic singlet oxygen ((1)O2) by irradiation with red laser was monitored using 1.3-diphenylisobenzofuran as a probe. The singlet oxygen quantum yields (ΦΔ) for ZnPc loaded chitosan nanocapsules were high and similar to that of the standard (ZnPc in DMSO), displaying excellent ability to generate (1)O2. The photosensitizer loaded nanocapsules are photostable in the timescale usually utilized in PDT and only a small photobleaching event was observed when a light dose of 610J/cm(2) was applied. The in vitro drug release studies of ZnPc from all nanocapsules demonstrated a sustained release profile controlled by diffusion, without burst effect. The nature of the polymer and the core type of the nanocapsules regulated ZnPc release. Thus, the nanocapsules developed in this work are a promising strategy to be employed in PDT. Copyright © 2015. Published by Elsevier B.V.

Photodegradation of microcystin-LR catalyzed by metal phthalocyanines immobilized on TiO2-SiO2 under visible-light irradiation.

PubMed

Peng, Guotao; Fan, Zhengqiu; Wang, Xiangrong; Sui, Xin; Chen, Chen

2015-01-01

Microcystins (MCs) are a group of monocyclic heptapeptide toxins produced by species of cyanobacteria. Since MCs exhibit acute and chronic effects on humans and wildlife by damaging the liver, they are of increasing concern worldwide. In this study, we investigated the ability of the phthalocyanine compound (ZnPc-TiO2-SiO2) to degrade microcystin-LR (MC-LR) in the presence of visible light. X-ray diffraction (XRD) and UV-Visible diffuse reflectance spectra (UV-Vis DRS) were utilized to characterize the crystalline phase and the absorption behavior of this catalyst. According to the results, XRD spectra of ZnPc-TiO2-SiO2 powders taken in the 2θ configuration exhibited the peaks characteristic of the anatase phase. UV-Vis DRS showed that the absorption band wavelength shifted to the visible range when ZnPc was supported on the surface of TiO2-SiO2. Subsequently, several parameters including catalyst dose, MC-LR concentrations and pH were investigated. The MC-LR was quantified in each sample through high-performance liquid chromatography (HPLC). The maximum MC-LR degradation rate of 80.2% can be obtained within 300 minutes under the following conditions: catalyst dose of 7.50 g/L, initial MC-LR concentration of 17.35 mg/L, pH 6.76 and the first cycling run of the photocatalytic reaction. Moreover, the degradation process fitted well with the pseudo-first-order kinetic model.

Highly efficient photodynamic therapy colloidal system based on chloroaluminum phthalocyanine/pluronic micelles.

PubMed

Py-Daniel, Karen R; Namban, Joy S; de Andrade, Laise R; de Souza, Paulo E N; Paterno, Leonardo G; Azevedo, Ricardo B; Soler, Maria A G

2016-06-01

Phthalocyanine derivatives comprise the second generation of photosensitizer molecules employed in photodynamic therapy (PDT) and have attracted much attention due to their outstanding photosensitizing performance. Most phthalocyanines are hydrophobic compounds that require association to drug delivery systems for clinical use. In this study, formulations of Pluronic F127 micelles incorporated with chloroaluminum phthalocyanine, or else F127/AlClPc, were produced at optimized conditions aiming at efficient and biocompatible PDT colloidal systems. Absorption/emission spectroscopies, as well as dynamic light scattering were performed to evaluate the optimum conditions for the F127 micelle formation and AlClPc incorporation. The micelles formation was attained with F127 concentrations ranging from 50 to 150mgmL(-1). At these conditions, AlClPc photosensitizer molecules were encapsulated into the hydrophobic micelle core and, therefore, readily solubilized in physiological medium (PBS pH 7.2). Encapsulation efficiency of about 90% resulted from different AlClPc concentrations. Identification of singlet oxygen production by irradiated F127/AlClPc formulations indicated good applicability for PDT. In vitro tests conducted with A549 human lung carcinoma cell line incubated with the F127/AlClPc formulations, at different AlClPc loadings, followed by only 18min of light irradiation (660nm LED, fluence of 25.3J/cm(2)), showed a cellular damage as high as 90% for rather low dosages of AlClPc (0.1-5.0μgmL(-1)). Further, no cytotoxicity occurred on non-irradiated cells. These findings suggest those F127/AlClPc formulations are highly promising for PDT applications, since they are easily prepared and the incubation and irradiation times are significantly shortened. Copyright © 2016 Elsevier B.V. All rights reserved.

Al(III), Pd(II), and Zn(II) phthalocyanines for inactivation of dental pathogen Aggregatibacter actinomycetemcomitans as planktonic and biofilm-cultures

NASA Astrophysics Data System (ADS)

Kussovski, V.; Mantareva, V.; Angelov, I.; Avramov, L.; Popova, E.; Dimitrov, S.

2012-06-01

The Gram-negative, oral bacterium Aggregatibacter actinomycetemcomitans has been implicated as the causative agent of several forms of periodontal disease in humans. The new periodontal disease treatments are emergence in order to prevent infection progression. Antimicrobial photodynamic therapy (a-PDT) can be a useful tool for this purpose. It involves the use of light of specific wavelength to activate a nontoxic photosensitizing agent in the presence of oxygen for eradication of target cells, and appears effective in photoinactivation of microorganisms. The phthalocyanine metal complexes of Pd(II)- (PdPcC) and Al(III)- (AlPc1) were evaluated as photodynamic sensitizers towards a dental pathogen A. actinomycetemcomitans in comparison to the known methylpyridyloxy-substituted Zn(II) phthalocyanine (ZnPcMe). The planktonic and biofilm-cultivated species of A. actinomycetemcomitans were treated. The photophysical results showed intensive and far-red absorbance with high tendency of aggregation for Pd(II)-phthalocyanine. The dark toxicities of both photosensitizers were negligible at concentrations used (< 0.5 log decrease of viable cells). The photodynamic response for planktonic cultured bacteria was full photoinactivation after a-PDT with ZnPcMe. In case of the newly studied complexes, the effect was lower for PdPcC (4 log) as well as for AlPc1 (1.5-2 log). As it is known the bacterial biofilms were more resistant to a-PDT, which was confirmed for A. actinomycetemcomitans biofilms with 3 log reductions of viable cells after treatment with ZnPcMe and approximately 1 log reduction of biofilms after PdPcC and AlPc1. The initial results suggest that a-PDT can be useful for effective inactivation of dental pathogen A. actinomycetemcomitans.

Mechanically Robust 3D Nanostructure Chitosan-Based Hydrogels with Autonomic Self-Healing Properties.

PubMed

Karimi, Ali Reza; Khodadadi, Azam

2016-10-12

Fabrication of hydrogels based on chitosan (CS) with superb self-healing behavior and high mechanical and electrical properties has become a challenging and fascinating topic. Most of the conventional hydrogels lack these properties at the same time. Our objectives in this research were to synthesize, characterize, and evaluate the general properties of chitosan covalently cross-linked with zinc phthalocyanine tetra-aldehyde (ZnPcTa) framework. Our hope was to access an unprecedented self-healable three-dimensional (3D) nanostructure that would harvest the superior mechanical and electrical properties associated with chitosan. The properties of cross-linker such as the structure, steric effect, and rigidity of the molecule played important roles in determining the microstructure and properties of the resulting hydrogels. The tetra-functionalized phthalocyanines favor a dynamic Schiff-base linkage with chitosan to form a 3D porous nanostructure. Based on this strategy, the self-healing ability, as demonstrated by rheological recovery and macroscopic and microscopic observations, is introduced through dynamic covalent Schiff-base linkage between NH 2 groups in CS and benzaldehyde groups at cross-linker ends. The hydrogel was characterized using FT-IR, NMR, UV/vis, and rheological measurements. In addition, cryogenic scanning electron microscopy (cryo-SEM) was employed as a technique to visualize the internal morphology of the hydrogels. Study of the surface morphology of the hydrogel showed a 3D porous nanostructure with uniform morphology. Furthermore, incorporating the conductive nanofillers, such as carbon nanotubes (CNTs), into the structure can modulate the mechanical and electrical properties of the obtained hydrogels. Interestingly, these hydrogel nanocomposites proved to have very good film-forming properties, high modulus and strength, acceptable electrical conductivity, and excellent self-healing properties at neutral pH. Such properties can be finely tuned through variation of the cross-linker and CNT concentration, and as a result these structures are promising candidates for potential applications in various fields of research.

Zinc phthalocyanine nanowires based flexible sensor for room temperature Cl2 detection

NASA Astrophysics Data System (ADS)

Devi, Pooja; Saini, Rajan; Singh, Rajinder; Mahajan, A.; Bedi, R. K.; Aswal, D. K.; Debnath, A. K.

2018-04-01

We have fabricated highly sensitive and Cl2 selective flexible sensor by depositing solution processed zinc phthalocyanine nanowires onto the flexible PET substrate and studied its Cl2 sensing characteristics in Cl2 concentration range 5-1500 ppb. The flexible sensor has a minimum detection limit as low as 5 ppb of Cl2 and response as high as 550% within 10 seconds. Interestingly, the sensor exhibited enhanced and faster response kinetics under bending conditions. The gas sensing mechanism of sensor has been discussed on the basis of XPS and Raman spectroscopic studies which revealed that zinc ions were the preferred sites for Cl2 interactions.

Tunneling electron induced chemisorption of copper phthalocyanine molecules on the Cu(111) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stock, T.; Nogami, J.

2014-02-17

The adsorption of up to one monolayer (ML) of copper phthalocyanine (CuPc) molecules on a room temperature Cu(111) surface has been studied using scanning tunneling microscopy (STM). Below 1 ML the molecules are in a fluid state and are highly mobile on the surface. At 1 ML coverage the molecules coalesce into a highly ordered 2D crystal phase. At sub-ML coverages, chemisorption of individual CuPc molecules can be induced through exposure to tunneling electrons at a tunneling bias voltage exceeding a threshold value. This tunneling electron induced effect has been exploited to perform molecular STM lithography.

Single crystal growth in spin-coated films of polymorphic phthalocyanine derivative under solvent vapor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Higashi, T.; Ohmori, M.; Ramananarivo, M. F.

2015-12-01

The effects of solvent vapor on spin-coated films of a polymorphic phthalocyanine derivative were investigated. Growth of single crystal films via redissolving organic films under solvent vapor was revealed by in situ microscopic observations of the films. X-ray diffraction measurement of the films after exposing to solvent vapor revealed the phase transition of polymorphs under solvent vapor. The direction of crystal growth was clarified by measuring the crystal orientation in a grown monodomain film. The mechanism of crystal growth based on redissolving organic films under solvent vapor was discussed in terms of the different solubilities of the polymorphs.

The photokilling of bladder carcinoma cells in vitro by phenothiazine dyes.

PubMed

Fowler, G J; Rees, R C; Devonshire, R

1990-09-01

The potential photodynamic therapy photosensitizers Methylene Blue, Azure C, Methylene Violet, Thionine, Methylene Green, Haematoporphyrin, Nile Blue A, chloroaluminium phthalocyanine and bis-aluminium phthalocyanine were examined for their photoeffects and dark toxicity against a human superficial bladder carcinoma cell-line. By examination of [3H]thymidine uptake into dye-treated cells after irradiation with a copper-vapour pumped dye laser, it was found that Methylene Blue was the most phototoxic and dark toxic of all the dyes tested, suggesting that the dye might be of some use as a topically applied photodrug for use in photodynamic therapy of superficial or early-recurring carcinomas.

Aluminum phthalocyanine tetrasulfonate in MCF-10F, human breast epithelial cells: a hole burning study.

PubMed Central

Milanovich, N; Reinot, T; Hayes, J M; Small, G J

1998-01-01

Laser-induced holes are burned in the absorption spectrum of aluminum phthalocyanine tetrasulfonate (APT) in MCF-10F, human breast epithelial cells. The hole burning mechanism is shown to be nonphotochemical. The fluorescence excitation spectra and hole spectra are compared with those of APT in hyperquenched glassy films of water, ethanol, and methanol. The results show that the APT is in an acidic, aqueous environment with a hydrogen-bonded network similar to that of glassy water, but showing the influence of other cellular components. Pressure shifts of holes allow the local compressibility about the APT to be determined. PMID:9591692

Unoccupied states in Cu and Zn octaethyl-porphyrin and phthalocyanine.

PubMed

Cook, Peter L; Yang, Wanli; Liu, Xiaosong; García-Lastra, Juan María; Rubio, Angel; Himpsel, F J

2011-05-28

Copper and zinc phthalocyanines and porphyrins are used in organic light emitting diodes and dye-sensitized solar cells. Using near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the Cu 2p and Zn 2p edges, the unoccupied valence states at the Cu and Zn atoms are probed and decomposed into 3d and 4s contributions with the help of density functional calculations. A comparison with the N 1s edge provides the 2p states of the N atoms surrounding the metal, and a comparison with inverse photoemission provides a combined density of states. © 2011 American Institute of Physics

Controlling molecular condensation/diffusion of copper phthalocyanine by local electric field induced with scanning tunneling microscope tip

NASA Astrophysics Data System (ADS)

Nagaoka, Katsumi; Yaginuma, Shin; Nakayama, Tomonobu

2018-02-01

We have discovered the condensation/diffusion phenomena of copper phthalocyanine (CuPc) molecules controlled with a pulsed electric field induced by the scanning tunneling microscope tip. This behavior is not explained by the conventional induced dipole model. In order to understand the mechanism, we have measured the electronic structure of the molecule by tunneling spectroscopy and also performed theoretical calculations on molecular orbitals. These data clearly indicate that the molecule is positively charged owing to charge transfer to the substrate, and that hydrogen bonding exists between CuPc molecules, which makes the molecular island stable.

Phthalo-carbonitride: an ab initio prediction of a stable two-dimensional material

NASA Astrophysics Data System (ADS)

Tsetseris, Leonidas

2016-06-01

Using density-functional theory calculations, we identify a stable two-dimensional carbonitride polymorph which resembles the core of phthalocyanine molecules. This so-called phthalo-carbonitride is found to be the lowest-energy polymer made of tetracyanoethylene molecules. It is a two-dimensional metal in its pristine form. Functionalization of the phthalo-cores with copper or iron atoms retains the metallic character of the material, but also adds magnetization to the system. Based on these properties and the established use of phthalocyanine molecules in various applications, the growth of phthalo-carbonitride sheets can add another multi-functional building block to the research and technology of two-dimensional materials.

Use of chloro-aluminum sulfonated phthalocyanine as a photosensitizer in the treatment of malignant tumors in dogs and cats

NASA Astrophysics Data System (ADS)

Peavy, George M.; Klein, Mary K.; Newman, H. C.; Roberts, Walter G.; Berns, Michael W.

1991-05-01

Chloro-aluminum sulfonated phthalocyanine (CASPc) has been proposed as a photosensitizing agent for photodynamic therapy (PDT) of neoplasia. This paper reviews the results of PDT treatment using CASPc as a photosensitizing agent in the treatment of 15 cats representing 23 sites of facial, solar induced squamous cell carcinoma, 4 dogs with hemangiopericytomas, 3 dogs with fibrosarcomas, and 1 dog with multiple cutaneous mast cell tumors. The results of this study to date suggest that CASPc is a good photosensitizing agent for the treatment of some forms of spontaneously occurring malignant neoplasia and should be more thoroughly evaluated for this purpose.

Photodynamic antimicrobial chemotherapy using zinc phthalocyanine derivatives in treatment of bacterial skin infection

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Zhang, Yaxin; Wang, Dong; Li, Linsen; Zhou, Shanyong; Huang, Joy H.; Chen, Jincan; Hu, Ping; Huang, Mingdong

2016-01-01

Photodynamic antimicrobial chemotherapy (PACT) is an effective method for killing bacterial cells in view of the increasing problem of multiantibiotic resistance. We herein reported the PACT effect on bacteria involved in skin infections using a zinc phthalocyanine derivative, pentalysine β-carbonylphthalocyanine zinc (ZnPc-Lys). Compared with its anionic ZnPc counterpart, ZnPc-Lys showed an enhanced antibacterial efficacy in vitro and in an animal model of localized infection. Meanwhile, ZnPc-Lys was observed to significantly reduce the wound skin blood flow during wound healing, indicating an anti-inflammation activity. This study provides new insight on the mechanisms of PACT in bacterial skin infection.

Spectroscopic and Electrochemical Studies of the Transition Metal Tetrasulfonated Phthalocyanines. Part 5. Voltammetric Studies of Adsorbed Tetrasulfonated Phthalocyanines (MTsPc) in Aqueous Solutions.

DTIC Science & Technology

1985-10-01

atmosphere Immediately after addition of M-TsPc to the supporting electrolyte, the first potential sweep over the given range (e.g., -0.8 to 0.3 V vs. SCE...vs. a-Pd/H electrode) at a sweep rate of 100 mV/s, voltammetric peaks of the hydrogen adsorption/desorption and oxide forma- tion/reduction processes...high sweep rates, e.g., 20 V/s. An OPG electrode standing at open-circuit potential in a Fe(III)-TsPc at potentials between peaks 3 and 4 in Fig. 1

Bulk functionalization of graphene using diazonium compounds and amide reaction

NASA Astrophysics Data System (ADS)

Peng, Chang; Xiong, Yuzi; Liu, Zhibo; Zhang, Fan; Ou, Encai; Qian, Jiangtao; Xiong, Yuanqin; Xu, Weijian

2013-09-01

An efficient and convenient method is applied to introduce varieties of simple functionalities onto the graphene surface for the bulk preparation, which begins with pristine graphite that does not require initial oxidative damage of the graphene basal planes. Diazonium compounds functionalized reaction is demonstrated and it successfully prevented the aggregation of graphene for which providing solubility in high polar organic media or even in volatile solvents such as ethanol and acetone. This approach is complemented by the phenyl carboxylic diazonium salt functionalized graphene (PCFG) attachment of a symmetrically substituted zinc phthalocyanine (PCFG-Pc) using the amide reaction, which is used for the covalent introduction of a complex phthalocyanine molecule.

Comparative study of different alcohol sensors based on Screen-Printed Carbon Electrodes.

PubMed

Costa Rama, Estefanía; Biscay, Julien; González García, María Begoña; Julio Reviejo, A; Pingarrón Carrazón, José Manuel; Costa García, Agustín

2012-05-30

Different very simple single-use alcohol enzyme sensors were developed using alcohol oxidase (AOX) from three different yeast, Hansenula sp., Pichia pastoris and Candida boidinii, and employing three different commercial mediator-based Screen-Printed Carbon Electrodes as transducers. The mediators tested, Prussian Blue, Ferrocyanide and Co-phthalocyanine were included into the ink of the working electrode. The procedure to obtain these sensors consists of the immobilization of the enzyme on the electrode surface by adsorption. For the immobilization, an AOX solution is deposited on the working electrode and left until dried (1h) at room temperature. The best results were obtained with the biosensor using Screen-Printed Co-phthalocyanine/Carbon Electrode and AOX from Hansenula sp. The reduced cobalt-phthalocyanine form is amperometrically detected at +0.4V (vs. Ag pseudo reference electrode). This sensor shows good sensitivity (1211 nA mM(-1)), high precision (2.1% RSD value for the slope value of the calibration plot) and wide linear response (0.05-1.00 mM) for ethanol determination. The sensor provides also accurate results for ethanol quantification in alcoholic drinks. Copyright © 2012 Elsevier B.V. All rights reserved.

Redox and fungicidal properties of phthalocyanine metal complexes as related to active oxygen.

PubMed

Vol'pin, M E; Novodarova, G N; Krainova NYu; Lapikova, V P; Aver'yanov, A A

2000-10-01

Some chemical and fungicidal effects of 20 phthalocyanines of Co, Fe, Cu, and Al were studied. Under dark conditions, these complexes reduced nitroblue tetrazolium in the presence of KCN, accelerated the autoxidation of ascorbate or hydroquinone and decomposed hydrogen peroxide. In the later reaction, hydroxyl radical was generated as evidenced with the deoxyribose assay. The inhibition by superoxide dismutase and catalase of catalyzed autoxidation of ascorbate suggests the participation of superoxide anion-radical and hydrogen peroxide in the reaction. Most complexes were toxic to the fungus Magnaporthe grisea which causes blast disease of rice. The toxicity was enhanced by light being diminished by antioxidant reagents sequestering active oxygen species. Some complexes (including nontoxic ones), after 1-day contact with a leaf surface of the disease-susceptible rice cultivar, induced the fungitoxicity of leaf diffusate. This toxicity was also light-activated and sensitive to antioxidant reagents. Several complexes, when added to inocula, decreased 2-3 times the frequency of the compatible symptoms of the blast. It is suggested that in planta, the dark redox activity of phthalocyanines along with their photosensitization promote the generation of active oxygen, which damages the parasite and, therefore, favors disease resistance.

Asymmetric Zinc Phthalocyanines as Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

Tunc, Gulenay; Yavuz, Yunus; Gurek, Aysegul; Canimkurbey, Betul; Kosemen, Arif; San, Sait Eren; Ahsen, Vefa

Dye-sensitized solar cells (DSSCs) have received increasing attention due to their high incident to photon efficiency, easy fabrication and low production cost . Tremendous research efforts have been devoted to the development of new and efficient sensitizers suitable for practical use. In TiO2-based DSSCs, efficiencies of up to 11.4% under simulated sunlight have been obtained with rutheniumepolypyridyl complexes. However, the main drawback of ruthenium complexes is the lack of absorption in the red region of the visible light and the high cost. For this reason, dyes with large and stable p-conjugated systems such as porphyrins and phthalocyanines are important classes of potential sensitizers for highly efficient DSSCs. Phthalocyanines (Pcs) have been widely used as sensitizers because of their improved light-harvesting properties in the far red- and near-IR spectral regions and their extraordinary robustness [1]. In this work, a series of asymmetric Zn(II) Pcs bearing a carboxylic acid group and six hexylthia groups either at the peripheral or non-peripheral positions have been designed and synthesized to investigate the influence of the COOH group and the positions of hexylthia groups on the dye-sensitized solar cell (DSSC) performance.

Formation of highly toxic hydrogen cyanide upon ruby laser irradiation of the tattoo pigment phthalocyanine blue.

PubMed

Schreiver, Ines; Hutzler, Christoph; Laux, Peter; Berlien, Hans-Peter; Luch, Andreas

2015-08-05

Since laser treatment of tattoos is the favored method for the removing of no longer wanted permanent skin paintings, analytical, biokinetics and toxicological data on the fragmentation pattern of commonly used pigments are urgently required for health safety reasons. Applying dynamic headspace-gas chromatography with mass spectrometric detection (DHS-GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC-ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension. Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue. Further, for the first time we introduce pyrolysis-GC/MS as method suitable to simulate pigment fragmentation that may occur spontaneously or during laser removal of organic pigments in the living skin of tattooed people. According to the literature such regular tattoos hold up to 9 mg pigment/cm(2) skin.

Formation of highly toxic hydrogen cyanide upon ruby laser irradiation of the tattoo pigment phthalocyanine blue

PubMed Central

Schreiver, Ines; Hutzler, Christoph; Laux, Peter; Berlien, Hans-Peter; Luch, Andreas

2015-01-01

Since laser treatment of tattoos is the favored method for the removing of no longer wanted permanent skin paintings, analytical, biokinetics and toxicological data on the fragmentation pattern of commonly used pigments are urgently required for health safety reasons. Applying dynamic headspace—gas chromatography with mass spectrometric detection (DHS—GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC—ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension. Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue. Further, for the first time we introduce pyrolysis-GC/MS as method suitable to simulate pigment fragmentation that may occur spontaneously or during laser removal of organic pigments in the living skin of tattooed people. According to the literature such regular tattoos hold up to 9 mg pigment/cm2 skin. PMID:26243473

Formation of highly toxic hydrogen cyanide upon ruby laser irradiation of the tattoo pigment phthalocyanine blue

NASA Astrophysics Data System (ADS)

Schreiver, Ines; Hutzler, Christoph; Laux, Peter; Berlien, Hans-Peter; Luch, Andreas

2015-08-01

Since laser treatment of tattoos is the favored method for the removing of no longer wanted permanent skin paintings, analytical, biokinetics and toxicological data on the fragmentation pattern of commonly used pigments are urgently required for health safety reasons. Applying dynamic headspace—gas chromatography with mass spectrometric detection (DHS—GC/MS) and comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GCxGC—ToF-MS), we identified 1,2-benzene dicarbonitrile, benzonitrile, benzene, and the poisonous gas hydrogen cyanide (HCN) as main fragmentation products emerging dose-dependently upon ruby laser irradiation of the popular blue pigment copper phthalocyanine in suspension. Skin cell viability was found to be significantly compromised at cyanide levels of ≥1 mM liberated during ruby laser irradiation of >1.5 mg/ml phthalocyanine blue. Further, for the first time we introduce pyrolysis-GC/MS as method suitable to simulate pigment fragmentation that may occur spontaneously or during laser removal of organic pigments in the living skin of tattooed people. According to the literature such regular tattoos hold up to 9 mg pigment/cm2 skin.

A Novel Gas Sensor Transducer Based on Phthalocyanine Heterojunction Devices

PubMed Central

Muzikante, Inta; Parra, Vicente; Dobulans, Rorijs; Fonavs, Egils; Latvels, Janis; Bouvet, Marcel

2007-01-01

Experimental data concerning the changes in the current-voltage (I-V) performances of a molecular material-based heterojunction consisting of hexadecafluorinated nickel phthalocyanine (Ni(F16Pc)) and nickel phthalocyanine (NiPc), (Au|Ni(F16Pc)|NiPc|Al) are introduced as an unprecedented principle of transduction for gas sensing performances. The respective n- and p-type doped-insulator behaviors of the respective materials are supported, owing to the observed changes in surface potential (using the Kelvin probe method) after submission to electron donor (ammonia) and electron acceptor gases (ozone). On the other hand, the bilayer device exhibits strong variations in the built-in potential of the junction and in its rectification ratio. Moreover, large increases occur in forward and reverse currents in presence of ammonia vapors. These make possible a multimodal principle of detection controlled by a combined effect between the heterojunction and the NiPc|Al contact. Indeed, this metal/organic junction plays a critical role regarding the steady asymmetry of the I-V profiles during the device's doping even using high ammonia concentrations. This approach offers a more sophisticated alternative to the classically studied, but at times rather operation-limited, resistive gas sensors. PMID:28903274

Infrared spectra of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes. Part 3. The effects of substituents and molecular symmetry on the infrared characteristics of phthalocyanine in bis(phthalocyaninato) rare earth complexes.

PubMed

Lu, Fanli; Bao, Meng; Ma, Changqin; Zhang, Xianxi; Arnold, Dennis P; Jiang, Jianzhuang

2003-12-01

The infra-red (IR) spectroscopic data for a series of 45 homoleptic unsubstituted and substituted bis(phthalocyaninato) rare earth complexes M(Pc)2 and M(Pc*)2 [M=Y, La...Lu except Pm; H2Pc=phthalocyanine; H2Pc*=2,3,9,10,16,17,24,25-octakis(octyloxy)phthalocyanine (H2OOPc) and 2(3),9(10),16(17),24(25)-tetra(tert-butyl)phthalocyanine (H2TBPc)] have been collected with resolution of 2 cm(-1). The IR spectra for M(Pc)2 and M(OOPc)2 are much simpler than those of M(TBPc)2, revealing the relatively higher symmetry of the former two compounds. For M(Pc)2 the Pc-* marker band at 1312-1323 cm(-1), attributed to the pyrrole stretching, and the isoindole stretching band at 1439-1454 cm(-1) are found to be dependent on the central rare earth size, shifting slightly to the higher energy along with the decrease of rare earth radius. The frequency of the vibration at 876-887 cm(-1) is also dependent on the rare earth ionic size. The metal size-sensitivity of this band and theoretical studies render it possible to re-assign it to the coupling of isoindole deformation and aza vibration. The nature of another metal-sensitive vibration mode at 1110-1116 cm(-1), which was previously assigned to the C-H bending, is now re-assigned as an isoindole breathing mode with some small contribution also from C-H in-plane bending. These assignments are supported by comparative studies of the IR spectra of substituted bis(phthalocyaninato) analogues M(OOPc)2 and M(TBPc)2. By comparison between the IR spectra of unsubstituted and substituted bis(phthalocyaninato) rare earth analogues and according to the IR characteristics of alkyl groups, some characteristic vibrational fundamentals due to the Pc rings and the substituents can be separately identified. In conclusion, all the metal size-dependent IR absorptions are composed primarily of the vibrations of pyrrole or isoindole stretching, breathing or deformation or aza stretching of the Pc ring.

Synthesis and Characterization of a Novel Polyacetal & Design and Preparation of Superhydrophobic Photocatalytic Surfaces

NASA Astrophysics Data System (ADS)

Zhao, Yuanyuan

Acetal copolymers represent a family of well-established engineering thermoplastics serving a broad range of important industrial applications including replacement for metals. The first part of this thesis describes the first synthesis of an eight-member ring acetal, 6-methyl-1, 3-dioxocane (MDOC), and its cationic copolymerization with trioxane initiated by boron trifluoride dibutyl etherate. The copolymerization process was monitored in situ using proton NMR. Incorporation of MDOC led to the insertion of the "stopper" unit, "--[CH2CH2CH(CH3)CH 2CH2)O]--", thus synthesizing the new acetal copolymer. A superior copolymer thermal stability with a ~ 20oC increase in degradation onset temperature compared with end-capped polyoxmethylene was observed. Both TGA and DSC data indicated the random placement of the "stopper" in the copolymer likely due to efficient transacetalization because of the higher basicity and flexibility of the stopper unit compared with co-units comprising 2 to 4 carbons in length. DSC thermo-grams showed a melting curve of a polymer with melting point lower, as expected, than that of oxymethylene homopolymer. No homopolymer in the copolymer samples was in indicated by TGA. The new acetal copolymer, poly(6-methyl-1,3-dioxocane-co-trioxane), which has a "stopper" co-unit with five carbon atoms along the backbone, contains the longest reported stopper co-unit, potentially leading to improved elongation, and toughness and better compatibility with a range of additives compared to acetal homopolymers.. Chapter 3 presents a novel lamination fabrication method that enables pre-formed TiO2 nanoparticles to become partially embedded in the surface of a thermoplastic polymer film. In this way, the particles are strongly adhered to the surface while remaining accessible to the aqueous solution. By modifying the fabrication conditions (e.g. temperature, pressure, polymer melt viscosity, etc.), the morphology of the hierarchical TiO2-polymer surface can be controlled and thus the rate of photocatalytic reactions can be increased. In addition, the fraction of TiO2 particles that become fully embedded in the polymer surface, and so inaccessible to photocatalysis reactions, can be reduced through lamination process control, thereby reducing costs. In Chapter 4 and Chapter 5, a general approach is presented to incorporating particles into a superhydrophobic surface that catalyze the formation of reactive oxygen species. Superhydrophobic photocatalytic surfaces are prepared using hydrophilic TiO2 nanoparticles and hydrophobic Silicon-Phthalocyanine photosensitizer particles. A stable Cassie state was maintained, even on surfaces fabricated with hydrophilic TiO2 particles, due to significant hierarchical roughness. A triple phase photogenerator is designed and fabricated. By printing the surface on a porous support, oxygen could be flowed through the plastron resulting in significantly higher photooxidation rates relative to a static ambient. Photooxidation of Rhodamine B and BSA were studied on TiO2-containing surfaces and singlet oxygen was trapped on surfaces incorporating Silicon-Phthalocyanine photosensitizer particles. Catalyst particles could be isolated in the plastron to avoid contamination by the solution. This approach may prove useful for water purification and medical devices where isolation of the catalyst particle from the solution is necessary and so Cassie stability is required. (Abstract shortened by UMI.).

Jeffrey Blackburn | NREL

Science.gov Websites

-dimensional carbon and includes the synthesis, purification, separation, and characterization of single-walled conversion Synthesis, purification, separation, and characterization of single-walled carbon nanotubes Synthesis, characterization, and device integration of graphen Hydrogen storage Photovoltaic materials and

Photoconductivity study of acid on Zinc phthalocyanine pyridine thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Sukhwinder, E-mail: ss7667@gmail.com; Saini, G. S. S.; Tripathi, S. K.

2016-05-06

The Metal Phthalocyanine (MPc) have attracted much interest because of chemical and high thermal stability. Molecules forming a crystal of MPc are held together by weak attractive Vander Waals forces. Organic semiconductors have π conjugate bonds which allow electrons to move via π-electron cloud overlaps. Conduction mechanisms for organic semiconductor are mainly through tunneling; hopping between localized states, mobility gaps, and phonon assisted hopping. The photo conductivity of thin films of these complexes changes when exposed to oxidizing and reducing gases. Arrhenius plot is used to find the thermal activation energy in the intrinsic region and impurity scattering region. Arrheniusmore » plotsare used to find the thermal activation energy.« less

High-efficiency THz modulator based on phthalocyanine-compound organic films

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Ting; Zhang, Bo, E-mail: bzhang@cnu.edu.cn, E-mail: sjl-phy@cnu.edu.cn; Shen, Jingling, E-mail: bzhang@cnu.edu.cn, E-mail: sjl-phy@cnu.edu.cn

2015-02-02

We report a high efficiency, broadband terahertz (THz) modulator following a study of phthalocyanine-compound organic films irradiated with an external excitation laser. Both transmission and reflection modulations of each organic/silicon bilayers were measured using THz time-domain and continuous-wave systems. For very low intensities, the experimental results show that AlClPc/Si can achieve a high modulation factor for transmission and reflection, indicating that AlClPc/Si has a superior modulation efficiency compared with the other films (CuPc and SnCl{sub 2}Pc). In contrast, the strong attenuation of the transmitted and reflected THz waves revealed that a nonlinear absorption process takes place at the organic/silicon interface.

Molecular orbital imaging of cobalt phthalocyanine on native oxidized copper layers using STM.

PubMed

Guo, Qinmin; Huang, Min; Qin, Zhihui; Cao, Gengyu

2012-07-01

To observe molecular orbitals using scanning tunneling microscopy, well-ordered oxidized layers on Cu(001) were fabricated to screen the individual adsorbed cobalt phthalocyanine (CoPc) molecules from the electronic influence of the metal surface. Scanning tunneling microscope images of the molecule on this oxidized layer show similarities to the orbital distribution of the free molecule. The good match between the differential conductance mapping images and the calculated charge distribution at energy levels corresponding to the frontier orbitals of CoPc provides more evidence of the screening of the oxidized layer from interactions between the metal surface and supported molecules. Copyright © 2012 Elsevier B.V. All rights reserved.

Dielectric response of branched copper phthalocyanine

NASA Astrophysics Data System (ADS)

Hamam, Khalil J.; Al-Amar, Mohammad M.; Mezei, Gellert; Guda, Ramakrishna; Burns, Clement A.

2017-09-01

The dielectric constant of pressed pellets and thin films of branched copper phthalocyanine (CuPc) was investigated as a function of frequency from 0.1 kHz to 1 MHz and temperature from 20 °C to 100 °C. Surface morphology was studied using a scanning electron microscope. The high-frequency values of the dielectric constant of pellets and thin films are ~3.5 and ~5.8, respectively. The response was only weakly dependent on frequency and temperature. The branched structure of the CuPc molecules helped to cancel out the effects of low-frequency polarization mechanisms. A planar delocalized charge system with two-dimensional localization was found using time-resolved photoluminescence measurements.

Room temperature ppb level Cl2 sensing using sulphonated copper phthalocyanine films.

PubMed

Kumar, Arvind; Singh, A; Debnath, A K; Samanta, S; Aswal, D K; Gupta, S K; Yakhmi, J V

2010-09-15

We present room temperature chemiresistive gas sensing characteristics of drop casted sulphonated copper phthalocyanine (CuTsPc) films. It has been demonstrated that these films are highly selective to Cl(2) and the sensitivity in the 5-2000 ppb range varies linearly between 65 and 625%. However, for concentrations >or=2000 ppb, the response becomes irreversible, which is found to be due to the chemical bond formation between Cl(2) and SO(3)Na group of CuTsPc films. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) data confirms the oxidation of SO(3)Na group by Cl(2) gas. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Nonequilibrium spin crossover in copper phthalocyanine

NASA Astrophysics Data System (ADS)

Siegert, Benjamin; Donarini, Andrea; Grifoni, Milena

2016-03-01

We demonstrate the nonequilibrium tip induced control of the spin state of copper phthalocyanine on an insulator coated substrate. We find that, under the condition of energetic proximity of many-body neutral excited states to the anionic ground state, the system can undergo a population inversion towards these excited states. The resulting state of the system is accompanied by a change in the total spin quantum number. Experimental signatures of the crossover are the appearance of additional nodal planes in the topographical scanning tunneling microscopy images as well as a strong suppression of the current near the center of the molecule. The robustness of the effect against moderate charge conserving relaxation processes has also been tested.

On the mechanism of pulsed laser ablation of phthalocyanine nanoparticles in an aqueous medium

NASA Astrophysics Data System (ADS)

Kogan, Boris; Malimonenko, Nicholas; Butenin, Alexander; Novoseletsky, Nicholas; Chizhikov, Sergei

2018-06-01

Laser ablation of phthalocyanine nanoparticles has potential for cancer treatment. The ablation is accompanied by the formation of microbubbles and the sublimation of nanoparticles. This was investigated in a liquid medium simulating tissue using optical-acoustic and spectral-luminescent methods. The thresholds for the appearance of microbubbles have been determined as a function of nanoparticle size. For the minimal size particles (80 nm) this threshold is equal to about 20–25 mJ cm‑2 and for the maximal size particles (230 nm) this threshold is equal to about 7 mJ cm‑2. It was estimated that the particle temperature at which bubbles arise is near 145 °С.

[Improvement of effectivity of photo disinfection of water from bacterial contaminants in the presence of heterogeneous sensitizers based on phthalocyanines grafted to aminopropyl silicagel].

PubMed

Maksimkina, T N; Artemova, T Z; Kuznetsova, N A; Sinitsyna, O O; Gipp, E K; Zagaĭnova, A V; Butorina, N N; Iuzhakova, O A; Krasniak, A V

2012-01-01

The possibility of using 12 heterogeneous sensitizers (HS) based on phthalocyanines covalently grafted to aminopropyl silicagel for disinfection of water from bacteria has been studied. For reliable water quality control the technique of performing bacteriological analysis in the presence of HS beads in the sample has been elaborated. The conditions increasing the efficiency of photo disinfection in the presence of HS were studied. Algorithm for estimation of photo disinfectant effect of HS against bacteria was substantiated. Obtained data confirm the perspective of further studies on the substantiation of the possibility of the application of HS for water disinfection.

Pressure-tuning micro-Raman spectra of artists' pigments: α- and β-copper phthalocyanine polymorphs.

PubMed

Beaulieu-Houle, Guillaume; Gilson, Denis F R; Butler, Ian S

2014-01-03

The two polymorphs of copper phthalocyanine, α- and β-CuPc, have been examined by micro-Raman spectroscopy at pressures approaching 5.0 GPa. The metastable α-polymorph does not exhibit any structural changes, while the more thermodynamically stable β-polymorph does exhibit a reversible phase transition at 2.0 GPa. The pressure dependences (dν/dP) for a selected number of vibrational modes are reported. Two regions of the Raman spectra, 800-900 cm(-1) and 1100-1200 cm(-1), are sensitive to pressure such that they can be used as indicators of the polymorphic form. Copyright © 2013 Elsevier B.V. All rights reserved.

Room Temperature ppb Level Chlorine Gas Sensor Based on Copper (II) 1, 4, 8, 11, 15, 18, 22, 25-octabutoxy-29 H, 31 H-phthalocyanine Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedi, R. K.; Saini, Rajan; Mahajan, Aman

2010-12-01

Spin coating technique has been used to fabricate room temperature chlorine gas sensor based on copper (II) 1, 4, 8, 11, 15, 18, 22, 25-octabutoxy-29 H, 31 H-phthalocyanine (CuPc(OBu){sub 8}) films. Gas sensor shows a response of 185% to few parts per billion level of Cl{sub 2} gas with response time of 9.5 minutes at room temperature. The interactions between sensor and analytes followed first order kinetics with rate constant 0.01{<=}k{<=}0.02. The chemiresistive sensor showed very good stability at room temperature over a long period of time.

Separation of porphyrin-based photosensitizer isomers by laser-induced fluorescence capillary electrophoresis.

PubMed

Peng, Xuejun; Sternberg, Ethan; Dolphin, David

2005-10-01

Methods for the separation of photosensitizer isomers, such as benzoporphyrin derivative monoacid, benzoporphyrin ethyl monoacid, 2-[1-hexyloxyethyl]-2-devinylpyropheophorbide-a, diethyleneglycol diester benzoporphyrin derivative, tin ethyl etiopurpurin, and phthalocyanine tetrasulfonate, have been systematically developed by CE. Detection was accomplished by UV absorption at 214 nm or by LIF with excitation at 442/488 nm and emission at 690 nm. The effects of three major experimental parameters of buffer types, organic solvents, and surfactant additives are described. The optimized separation conditions were determined so as to provide satisfactory separation efficiency and analysis time. The methods are shown to be suitable for the separation and determination of porphyrin and phthalocyanines regioisomers, diastereoisomers, and enantiomers.

Fabrication of a Quartz-Crystal-Microbalance/Optical-Waveguide Hybrid Sensor and In situ Evaluation of Vacuum-Evaporated Lead Phthalocyanine Thin Film

NASA Astrophysics Data System (ADS)

Shinbo, Kazunari; Uno, Akihiro; Hirakawa, Ryo; Baba, Akira; Ohdaira, Yasuo; Kato, Keizo; Kaneko, Futao

2013-05-01

In this study, we fabricated a novel quartz-crystal-microbalance (QCM)/optical-waveguide hybrid sensor. An in situ observation of a lead phthalocyanine (PbPc) thin-film deposition was conducted during vacuum evaporation, and the effectiveness of the sensor was demonstrated. The film thickness was obtained from the QCM frequency, and the optical absorption of the film was observed by optical waveguide spectroscopy using part of the QCM substrate without the electrode. The film absorption depends on the polarization direction, substrate temperature and deposition rate, owing to aggregate formation. The thickness dependence of the absorption property was also investigated.

A molecular heterojunction of zinc phthalocyanine and peanut-shaped fullerene polymer: A density functional study

NASA Astrophysics Data System (ADS)

Tanikawa, Kousei; Ohno, Kaoru; Noda, Yusuke; Ono, Shota; Kuwahara, Riichi; Takashima, Akito; Nakaya, Masato; Onoe, Jun

2017-10-01

We have performed first-principles density functional calculations of a molecular heterojunction of a zinc phthalocyanine (ZnPc) molecule and a peanut-shaped fullerene polymer (PSFP) made from several coalesced cross-linked C60 molecules. The PSFP has many isomers and all have both spatially localized (near ZnPc) and metallic conducting levels. Here we consider four typical isomers. From the resulting electronic structure, we discuss the applicability of these isomers to organic photovoltaics (OPV), electrodes, and light harvesting materials. If one of the isomers called T3, which has the largest energy gap, is used together with ZnPc for OPV, this system shows more than 20% energy conversion efficiency.

Influence of Molecular Orientation on Charge-Transfer Processes at Phthalocyanine/Metal Oxide Interfaces and Relationship to Organic Photovoltaic Performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Hsiao-Chu; MacDonald, Gordon A.; Shi, Yanrong

2015-05-04

The effect of the molecular orientation distribution of the first monolayer of donor molecules at the hole-harvesting contact in an organic photovoltaic (OPV) on device efficiency was investigated. Two zinc phthalocyanine (ZnPc) phosphonic acids (PA) deposited on indium tin oxide (ITO) electrodes are compared: ZnPc(PA)4 contains PA linkers in all four quadrants, and ZnPcPA contains a PA linker in one quadrant. ZnPcPA monolayers exhibited a broad distribution of molecular orientations whereas ZnPc(PA)4 adsorption produced a monolayer with a narrower orientation distribution with the molecular plane more parallel to the ITO surface. We used potential-modulated attenuated total reflectance spectroelectrochemistry (PM-ATR) tomore » characterize the charge-transfer kinetics of these films and show that the highest rate constants correspond to ZnPc subpopulations that are oriented more parallel to the ITO surface plane. For ZnPc(PA)4, rate constants exceeded 104 s–1 and are among the highest ever reported for a surface-confined redox couple, which is attributable to both its orientation and the small ZnPc–electrode separation distance. The performance of OPVs with ITO hole-harvesting contacts modified with ZnPc(PA)4 was comparable to that achieved with highly activated bare ITO contacts, whereas for ZnPcPA-modified contacts, the OPV performance was similar to that observed with (hole-blocking) alkyl-PA modifiers. These results demonstrate the synergism between molecular structure, energetics, and dynamics at interfaces in OPVs.« less

Thickness dependent charge transfer states and dark carriers density in vacuum deposited small molecule organic photocell

NASA Astrophysics Data System (ADS)

Shekhar, Himanshu; Tzabari, Lior; Solomeshch, Olga; Tessler, Nir

2016-10-01

We have investigated the influence of the active layer thickness on the balance of the internal mechanisms affecting the efficiency of copper phthalocyanine - fullerene (C60) based vacuum deposited bulk heterojunction organic photocell. We fabricated a range of devices for which we varied the thickness of the active layer from 40 to 120 nm and assessed their performance using optical and electrical characterization techniques. As reported previously for phthalocyanine:C60, the performance of the device is highly dependent on the active layer thickness and of all the thicknesses we tried, the 40 nm thin active layer device showed the best solar cell characteristic parameters. Using the transfer matrix based optical model, which includes interference effects, we calculated the optical power absorbed in the active layers for the entire absorption band, and we found that this cannot explain the trend with thickness. Measurement of the cell quantum efficiency as a function of light intensity showed that the relative weight of the device internal processes changes when going from 40 nm to 120 nm thick active layer. Electrical modeling of the device, which takes different internal processes into account, allowed to quantify the changes in the processes affecting the generation - recombination balance. Sub gap external quantum efficiency and morphological analysis of the surface of the films agree with the model's result. We found that as the thickness grows the density of charge transfer states and of dark carriers goes up and the uniformity in the vertical direction is reduced.

Interfacial Engineering of Perovskite Solar Cells by Employing a Hydrophobic Copper Phthalocyanine Derivative as Hole-Transporting Material with Improved Performance and Stability.

PubMed

Jiang, Xiaoqing; Yu, Ze; Lai, Jianbo; Zhang, Yuchen; Hu, Maowei; Lei, Ning; Wang, Dongping; Yang, Xichuan; Sun, Licheng

2017-04-22

In high-performance perovskite solar cells (PSCs), hole-transporting materials (HTMs) play an important role in extracting and transporting the photo-generated holes from the perovskite absorber to the cathode, thus reducing unwanted recombination losses and enhancing the photovoltaic performance. Herein, solution-processable tetra-4-(bis(4-tert-butylphenyl)amino)phenoxy-substituted copper phthalocyanine (CuPc-OTPAtBu) was synthesized and explored as a HTM in PSCs. The optical, electrochemical, and thermal properties were fully characterized for this organic metal complex. The photovoltaic performance of PSCs employing this CuPc derivative as a HTM was further investigated, in combination with a mixed-ion perovskite as a light absorber and a low-cost vacuum-free carbon as cathode. The optimized devices [doped with 6 % (w/w) tetrafluoro-tetracyano-quinodimethane (F4TCNQ)] showed a decent power conversion efficiency of 15.0 %, with an open-circuit voltage of 1.01 V, a short-circuit current density of 21.9 mA cm -2 , and a fill factor of 0.68. Notably, the PSC devices studied also exhibited excellent long-term durability under ambient condition for 720 h, mainly owing to the introduction of the hydrophobic HTM interlayer, which prevents moisture penetration into the perovskite film. The present work emphasizes that solution-processable CuPc holds a great promise as a class of alternative HTMs that can be further explored for efficient and stable PSCs in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation and Control of "Sphere-Like" Buckminsterfullerene C60 and "Disk-Like" Copper(II) Phthalocyanine

NASA Astrophysics Data System (ADS)

McAfee, Terry Richard

Due to the growing global need for cheap, flexible, and portable electronics, numerous research groups from mechanical and electrical engineering, material science, chemistry, and physics have increasingly turned to organic electronics research over the last ˜5--10 years. Largely, the focus of researchers in this growing field have sought to obtain the next record holding device, allowing a heuristic approach of trial and error to become dominant focus of research rather than a fundamental understanding. Rather than working with the latest high performance organic semiconducting materials and film processing techniques, I have chosen to investigate and control the fundamental self-assembly interactions of organic photovoltaic thin films using simplified systems. Specifically, I focus on organic photovoltaic research using two of the oldest and well studies semiconducting materials, namely "sphere-like" electron donor material Buckminsterfullerene C60 and "disklike" electron acceptor material Copper(II) Phthalocyanine. I manufactured samples using the well-known technique of physical vapor deposition using a high vacuum chamber that I designed and built to accommodate my need of precise material deposition control, with codeposition capability. Films were characterized using microscopy and spectroscopy techniques locally at NCSU, including Atomic Force Microscopy, scanning tunneling microscopy, X-ray photoelectron spectroscopy, and Ultraviolet-visible spectroscopy, as well as at National Laboratory based synchrotron x-ray techniques, including Carbon and Nitrogen k-edge Total Electron Yield and Transmission Near Edge X-ray absorption fine structure spectroscopy, Carbon k-edge Resonant Soft x-ray Microscopy, Resonant Soft x-ray reflectivity, and Grazing Incidence Wide-Angle X-ray scattering.

Construction and electrochemical characterization of microelectrodes for improved sensitivity in paper-based analytical devices

PubMed Central

Santhiago, Murilo; Wydallis, John B.; Kubota, Lauro T.; Henry, Charles S.

2013-01-01

This work presents a simple, low cost method for creating microelectrodes for electrochemical paper-based analytical devices (ePADs). The microelectrodes were constructed by backfilling small holes made in polyester sheets using a CO2 laser etching system. To make electrical connections, the working electrodes were combined with silver screen-printed paper in a sandwich type two-electrode configuration. The devices were characterized using linear sweep voltammetry and the results are in good agreement with theoretical predictions for electrode size and shape. As a proof-of-concept, cysteine was measured using cobalt phthalocyanine as a redox mediator. The rate constant (kobs) for the chemical reaction between cysteine and the redox mediator was obtained by chronoamperometry and found to be on the order of 105 s−1 M−1. Using a microelectrode array, it was possible to reach a limit of detection of 4.8 μM for cysteine. The results show that carbon paste microelectrodes can be easily integrated with paper-based analytical devices. PMID:23581428

Construction and electrochemical characterization of microelectrodes for improved sensitivity in paper-based analytical devices.

PubMed

Santhiago, Murilo; Wydallis, John B; Kubota, Lauro T; Henry, Charles S

2013-05-21

This work presents a simple, low cost method for creating microelectrodes for electrochemical paper-based analytical devices (ePADs). The microelectrodes were constructed by backfilling small holes made in polyester sheets using a CO2 laser etching system. To make electrical connections, the working electrodes were combined with silver screen-printed paper in a sandwich type two-electrode configuration. The devices were characterized using linear sweep voltammetry, and the results are in good agreement with theoretical predictions for electrode size and shape. As a proof-of-concept, cysteine was measured using cobalt phthalocyanine as a redox mediator. The rate constant (k(obs)) for the chemical reaction between cysteine and the redox mediator was obtained by chronoamperometry and found to be on the order of 10(5) s(-1) M(-1). Using a microelectrode array, it was possible to reach a limit of detection of 4.8 μM for cysteine. The results show that carbon paste microelectrodes can be easily integrated with paper-based analytical devices.

Hexagonal mesoporous silica modified with copper phthalocyanine as a photocatalyst for pesticide 2,4-dichlorophenoxiacetic acid degradation.

PubMed

DeOliveira, Edimar; Neri, Cláudio R; Ribeiro, Anderson O; Garcia, Vinícius S; Costa, Leonardo L; Moura, Aline O; Prado, Alexandre G S; Serra, Osvaldo A; Iamamoto, Yassuko

2008-07-01

A new mesoporous catalyst was prepared by the reaction between 3-aminopropyltrimethoxisylane and Cu(II)-hexadecafluorophthalocyanine, followed by co-condensation of tetraethylorthosilicate around a micelle formed by n-dodecylamine. The surfactant was removed from the pores by continuous extraction with ethanol, giving the Si-CuF16Pc catalyst. This catalyst was characterized by SEM, FTIR, TGA, 29Si NMR, N2 adsorption and X-ray diffraction. SEM images confirmed that the catalyst material is formed by nanoaggregates with a diameter of 100 nm. N2 adsorption isotherms showed that Si-CuF16Pc has a surface area of approximately 200 m2 g(-1) and a porous diameter of 7.7 nm, characterizing the mesoporosity of this product. This novel material shows an excellent photocatalytic activity, degrading almost 90% of 2,4-dichlorophenoxyacetic acid (2,4-D) up to 30 min, while only approximately 40% of photodegradation was obtained in its absence.

Accessing Synthetically-Challenging Isoindole-Based Materials for Assessment in Organic Photovoltaics via Chemical and Engineering Methodologies =

NASA Astrophysics Data System (ADS)

Dang, Jeremy

Isoindoles are a broad class of compounds that comprise a very small space within the domain of established photoactive materials for organic photovoltaics (OPVs). Given this scarcity, combined with the performance appeal of presently and well known isoindole-based compounds such as the phthalocyanines, it is a worthy undertaking to develop new materials in this domain. This thesis aims to bring to light the suitability of five novel, or underexplored, classes of isoindole-based materials for OPVs. These classes are the boron subphthalocyanine (BsubPc) polymers, oxygen-bridged dimers of BsubPcs (mu-oxo-(BsubPc) 2), boron subnaphthalocyanines (BsubNcs), group XIII metal complexes of 1,3-bis(2-pyridylimino)isodinoline (BPI), and the boron tribenzosubporphyrins (BsubPys). The synthesis of these materials was proven to be challenging as evident in their low isolated yields, lengthy synthetic and purification processes, and/or batch-to-batch variations. This outcome was not surprising given their undeveloped chemical nature. The photo- and electro-physical properties were characterized and shown to be desirable for all classes other than the group XIII metal complexes of BPI for OPVs. mu-Oxo-(BsubPc)2 and BsubNcs show promise in this application while BsubPc polymers and BsubPys will be subjects of future exploration. The results from the work herein aid to develop and strengthen the fundamental understanding of the structure-property relationships of isoindole derivatives. On a broader scale, the work demonstrates their versatility as functional materials for OPVs and their possible expansion to other organic electronic technologies like organic light emitting diodes and organic field effect transistors.

The effect of coadsorbent and solvent on the photovoltaic performance of 2,9,16,23-Tetrakis(7-coumarinoxy-4-methyl)-phthalocyaninatocopper-sensitized solar cells

NASA Astrophysics Data System (ADS)

Zhang, Fei; Wang, Shi-Rong; Li, Xiang-Gao; Xiao, Yin; Guo, Jun-Jie

2016-03-01

The synthesis, characterization and thermal properties of CuPc-Cou were reported and the effects of chenodeoxycholic acid (CHENO) as a coadsorbent and the solvent on the solar cell's performance were investigated. The ground state absorbance of CuPc-Cou showed the molar extinction coefficients as high as 2.90 × 104 dm3 mol-1 cm-1 in DMF and 2.74 × 104 dm3 mol-1 cm-1 in CH2Cl2. The thermal stability studies indicated that CuPc-Cou was stable up to 370 °C. Furthermore, HOMO and LUMO energies made it clear that CuPc-Cou can be used as a sensitizer for DSSC. Adding CHENO onto TiO2 nanoparticles not only reduced the adsorption of phthalocyanine sensitizers but also prevented the aggregation behavior, leading to different photovoltaic performance. The open circuit voltage of the solar cells with CHENO coadsorbent increased due to the enhanced electron lifetime in TiO2 nanoparticles coupled with the band edge shift of TiO2 to negative potentials. The optimal dye adsorption condition of the TiO2 electrode was found to be 3 × 10-4 M CuPc-Cou solution containing 6.0 mM CHENO in dichloromethane, which could contribute to improve the PCE by 69% as compared to the solar cell fabricated with TiO2 electrode sensitized by the CuPc-Cou in absence of CHENO and the optimal condition in DMF. It indicated that CuPc-Cou in DMF was easy to aggregate than in CH2Cl2 for the solvent effect.

Prevention of poxvirus infection by tetrapyrroles

PubMed Central

Chen-Collins, Avril RM; Dixon, Dabney W; Vzorov, Andrei N; Marzilli, Luigi G; Compans, Richard W

2003-01-01

Background Prevention of poxvirus infection is a topic of great current interest. We report inhibition of vaccinia virus in cell culture by porphyrins and phthalocyanines. Most previous work on the inhibition of viruses with tetrapyrroles has involved photodynamic mechanisms. The current study, however, investigates light-independent inhibition activity. Methods The Western Reserve (WR) and International Health Department-J (IHD-J) strains of vaccinia virus were used. Virucidal and antiviral activities as well as the cytotoxicity of test compounds were determined. Results Examples of active compounds include zinc protoporphyrin, copper hematoporphyrin, meso(2,6-dihydroxyphenyl)porphyrin, the sulfonated tetra-1-naphthyl and tetra-1-anthracenylporphyrins, selected sulfonated derivatives of halogenated tetraphenyl porphyrins and the copper chelate of tetrasulfonated phthalocyanine. EC50 values for the most active compounds are as low as 0.05 µg/mL (40 nM). One of the most active compounds was the neutral meso(2,6-dihydroxyphenyl)porphyrin, indicating that the compounds do not have to be negatively charged to be active. Conclusions Porphyrins and phthalocyanines have been found to be potent inhibitors of infection by vaccinia virus in cell culture. These tetrapyrroles were found to be active against two different virus strains, and against both enveloped and non-enveloped forms of the virus, indicating that these compounds may be broadly effective in their ability to inhibit poxvirus infection. PMID:12773208

Supramolecular complex of a fused zinc phthalocyanine-zinc porphyrin dyad assembled by two imidazole-C60 units: ultrafast photoevents.

PubMed

Follana-Berná, Jorge; Seetharaman, Sairaman; Martín-Gomis, Luis; Charalambidis, Georgios; Trapali, Adelais; Karr, Paul A; Coutsolelos, Athanassios G; Fernández-Lázaro, Fernando; D'Souza, Francis; Sastre-Santos, Ángela

2018-03-14

A new zinc phthalocyanine-zinc porphyrin dyad (ZnPc-ZnP) fused through a pyrazine ring has been synthesized as a receptor for imidazole-substituted C 60 (C 60 Im) electron acceptor. Self-assembly via metal-ligand axial coordination and the pertinent association constants in solution were determined by 1 H-NMR, UV-Vis and fluorescence titration experiments at room temperature. The designed host was able to bind up to two C 60 Im electron acceptor guest molecules to yield C 60 Im:ZnPc-ZnP:ImC 60 donor-acceptor supramolecular complex. The spectral data showed that the two binding sites behave independently with binding constants similar in magnitude. Steady-state fluorescence studies were indicative of an efficient singlet-singlet energy transfer from zinc porphyrin to zinc phthalocyanine within the fused dyad. Accordingly, the transient absorption studies covering a wide timescale of femto-to-milli seconds revealed ultrafast energy transfer from 1 ZnP* to ZnPc (k EnT ∼ 10 12 s -1 ) in the fused dyad. Further, a photo induced electron transfer was observed in the supramolecularly assembled C 60 Im:ZnPc-ZnP:ImC 60 donor-acceptor complex leading to charge separated states, which persisted for about 200 ns.

Inhibition of protease-resistant prion protein formation by porphyrins and phthalocyanines

PubMed Central

Caughey, Winslow S.; Raymond, Lynne D.; Horiuchi, Motohiro; Caughey, Byron

1998-01-01

A central aspect of pathogenesis in the transmissible spongiform encephalopathies or prion diseases is the conversion of normal protease-sensitive prion protein (PrP-sen) to the abnormal protease-resistant form, PrP-res. Here we identify porphyrins and phthalocyanines as inhibitors of PrP-res accumulation. The most potent of these tetrapyrroles had IC50 values of 0.5–1 μM in scrapie-infected mouse neuroblastoma (ScNB) cell cultures. Inhibition was observed without effects on protein biosynthesis in general or PrP-sen biosynthesis in particular. Tetrapyrroles also inhibited PrP-res formation in a cell-free reaction composed predominantly of hamster PrP-res and PrP-sen. Inhibitors were found among phthalocyanines, deuteroporphyrins IX, and meso-substituted porphines; examples included compounds containing anionic, neutral protic, and cationic peripheral substituents and various metals. We conclude that certain tetrapyrroles specifically inhibit the conversion of PrP-sen to PrP-res without apparent cytotoxic effects. The inhibition observed in the cell-free conversion reaction suggests that the mechanism involved direct interactions of the tetrapyrrole with PrP-res and/or PrP-sen. These findings introduce a new class of inhibitors of PrP-res formation that represents a potential source of therapeutic agents for transmissible spongiform encephalopathies. PMID:9770449

Photochemistry of transition-metal phthalocyanines. Analysis of the photochemical and photophysical properties of the acido(phthalocyaninato)rhodium(III) complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferraudi, G.; Muralidharan, S.

1983-04-01

The ultraviolet photochemistry of the rhodium(II) phthalocyanines Rh(ph)(CH/sub 3/OH)X with X = Cl/sup -/, Br/sup -/, and I/sup -/ was investigated at different wavelengths. The same action spectrum for the photoinduced hydrogen abstraction was obtained for the three compounds. The photonic energy of the excitation is degraded in part by emission at short wavelengths, e.g. lambda/sub max/ approx. = 420 nm. Such a violet emission, observed with phthalocyanines of Al(III), Rh(III), Co(III), and Ru(II), has been attributed to the relaxation of an upper /sup 3/par. deltapar. delta* excited state. The emissions spectra at 77 K exhibited vibronic components with amore » separation between successive peaks ..delta nu.. approx. = 1.3 x 10/sup 3/ cm/sup -1/. A comparison between the excitation and action spectra shows the difference in the paths that populate the reactive npar. delta* and upper emissive par. deltapar. delta* states. An investigation of the time dependence of the upper /sup 3/par. deltapar. delta* emission and lowest /sup 3/par. deltapar. delta* absorptions reveals the participation of triplet sublevels in the degradation of the excitation energy. The relationship between photoemissive and photoreactive states is discussed.« less

Photochemistry of transition-metal phthalocyanines. Analysis of the photochemical and photophysical properties of the acido(phthalocyaninato)rhodium(III) complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferraudi, G.; Muralidharan, S.

1983-01-01

The ultraviolet photochemistry of the rhodium(III) phthalocyanines Rh(ph)(CH/sub 3/OH)X with X = Cl/sup -/, Br/sup -/, and I/sup -/ was investigated at different wavelengths. The same action spectrum for the photoinduced hydrogen abstraction was obtained for the three compounds. The photonic energy of the excitation is degraded in part by emission at short wavelengths, e.g. lambda/sub max/ approx. = 420 nm. Such a violet emission, observed with phthalocyanines of Al(III), Rh(III), Co(III), and Ru(II), has been attributed to the relaxation of an upper /sup 3/pipi* excited state. The emission spectra at 77 K exhibited vibronic components with a separation betweenmore » successive peaks ..delta..v approx. = 1.3 x 10/sup 3/ cm/sup -1/. A comparison between the excitation and action spectra shows the difference in the paths that populate the reactive npi* and upper emissive pipi* states. An investigation of the time dependence of the upper /sup 3/pipi* emission and lowest /sup 3/pipi* absorptions reveals the participation of triplet sublevels in the degradation of the excitation energy. The relationship between photoemissive and photoreactive states is discussed. 40 references, 6 figures, 2 tables.« less

Plasmon-enhanced photocurrent generation from self-assembled monolayers of phthalocyanine by using gold nanoparticle films.

PubMed

Sugawa, Kosuke; Akiyama, Tsuyoshi; Kawazumi, Hirofumi; Yamada, Sunao

2009-04-09

The effect of localized electric fields on the photocurrent responses of phthalocyanine that was self-assembled on a gold nanoparticle film was investigated by comparing the conventional and the total internal reflection (TIR) experimental systems. In the case of photocurrent measurements, self-assembled monolayers (SAMs) of a thiol derivative of palladium phthalocyanine (PdPc) were prepared on the surface of gold-nanoparticle film that was fixed on the surface of indium-tin-oxide (ITO) substrate via a polyion (PdPc/AuP/polyion/ITO) or on the ITO surface (PdPc/ITO). Photocurrent action spectra from the two samples were compared by using the conventional spectrometer, and were found that PdPc/AuP/polyion/ITO gave considerably larger photocurrent signals than PdPc/ITO under the identical concentration of PdPc. In the case of the TIR experiments for the PdPc/AuP/polyion/ITO and the PdPc/AuP/Glass systems, incident-angle profiles of photocurrent and emission signals were correlated with each other, and they were different from that of the PdPc/ITO system. Accordingly, it was demonstrated that the photocurrent signals were certainly enhanced by the localized electric fields of the gold-nanoparticle film.

Iron(III) phthalocyanine supported on a spongin scaffold as an advanced photocatalyst in a highly efficient removal process of halophenols and bisphenol A.

PubMed

Norman, Małgorzata; Żółtowska-Aksamitowska, Sonia; Zgoła-Grześkowiak, Agnieszka; Ehrlich, Hermann; Jesionowski, Teofil

2018-04-05

This study investigated for the first time the degradation of phenol, chlorophenol, fluorophenol and bisphenol A (BPA) by the novel iron phthalocyanine/spongin hybrid material under various process conditions: hydrogen peroxide and UV irradiation. The heterogeneous catalyst, iron phthalocyanine/spongin (SFe), was produced by an adsorption process. The product obtained was investigated by a variety of spectroscopic techniques - X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) and carbon-13 nuclear magnetic resonance ( 13 C NMR) - as well as elemental and thermal analysis. The study confirmed the stable immobilization of the dye on the biopolymer. The results demonstrate that the degradation of phenols and BPA followed pseudo-second-order kinetics under different experimental conditions. The synergy of SFe, H 2 O 2 and UV was found to produce a significant increase in the removal efficiency and resulted in complete removal of contaminants in a short time of 1 h. The reaction products were identified by high-performance liquid chromatography/mass spectrometry (HPLC-MS) and possible degradation pathways were proposed, featuring a series of steps including cleavage of CC bonds and oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

The Effect of Gravity Axis Orientation on the Growth of Phthalocyanine Thin Films

NASA Technical Reports Server (NTRS)

Pearson, Earl F.

1996-01-01

Experimentally, many of the functions of electrical circuits have been demonstrated using optical circuits and, in theory, all of these functions may be accomplished using optical devices made of nonlinear optical materials. Actual construction of nonlinear optical devices is one of the most active areas in all optical research being done at this time. Physical vapor transport (PVT) is a promising technique for production of thin films of a variety of organic and inorganic materials. Film optical quality, orientation of microcrystals, and thickness depends critically on type of material, pressure of buffer gas and temperature of deposition. An important but understudied influence on film characteristics is the effect of gravity-driven buoyancy. Frazier, Hung, Paley, Penn and Long have recently reported mathematical modelling of the vapor deposition process and tested the predictions of the model on the thickness of films grown by PVT of 6-(2-methyl-4-nitroanilino)-2,4-hexadiyn-l-ol (DAMNA). In an historic experiment, Debe, et. al. offered definitive proof that copper phthalocyanine films grown in a low gravity environment are denser and more ordered than those grown at 1 g. This work seeks to determine the influence on film quality of gravity driven buoyancy in the low pressure PVT film growth of metal-free phthalocyanine.

High-potential perfluorinated phthalocyanine-fullerene dyads for generation of high-energy charge-separated states: formation and photoinduced electron-transfer studies.

PubMed

Das, Sushanta K; Mahler, Andrew; Wilson, Angela K; D'Souza, Francis

2014-08-25

High oxidation potential perfluorinated zinc phthalocyanines (ZnF(n)Pcs) are synthesised and their spectroscopic, redox, and light-induced electron-transfer properties investigated systematically by forming donor-acceptor dyads through metal-ligand axial coordination of fullerene (C60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine- (Py) and phenylimidazole-functionalised fullerene (C60Im) derivatives to the zinc centre of the F(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) M(-1); nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6-31G* method. The HOMO and LUMO levels are located on the Pc and C60 entities, respectively; this suggests the formation of ZnF(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-C60Py(.-) (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C60 dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge-separated states. The energy of the charge-separated state for dyads composed of ZnF(n)Pc is higher than that of normal ZnPc-C60 dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar-energy harvesting and optoelectronic device building applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Micro-Encapsulated Porphyrins and Phthalocyanines - New Formulations in Photodynamic Therapy

NASA Astrophysics Data System (ADS)

Ion, R. M.

2017-06-01

Photodynamic therapy (PDT), as an innovative method for cancer tretament is based on a concerted action of some drugs, called sensitizers, which generate reactive oxygen species via a photochemical mechanism, leading to cellular necrosis or apoptosis. The present work aims at loading some sensitizers, as porphyrins (P) and phthalocyanines (Pc) into alginate particles. Particles were prepared by dropping alginate into an aqueous solution containing P or Pc and CaCl2, which allows the formation of particles through ionic crosslinking. It was obtained P or Pc loaded alginate beads with an average diameter of about 100 μm. For these systems, this paper analyses the spectroscopic properties, encapsulation into microcapsules, controlled releasing action and their photosensitizer capacity (singlet oxygen generation).

Dielectric studies of boron sub phthalocyanine chloride thin films by admittance spectroscopic techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalia, Sameer; Neerja; Mahajan, Aman, E-mail: dramanmahajan@yahoo.co.in

The dielectric properties of Boron Sub Phthalocyanine Chloride (Cl-SubPc) thermally deposited on ITO substrate have been studied using admittance spectroscopic techniques. The I-V and capacitance –frequency (C-F) studies at various bias voltages reveal that the mobility of charge carriers decrease with bias voltage, however the conduction phenomenon still remain hopping in nature. From the differential susceptance curve, the contribution of the Schottky barrier contact in the charge carrier concentration was found to be absent. The mobility of charge carriers have been determined using differential susceptance variation and from the phase of admittance curve. The values obtained in two cases havemore » been found to be in agreement with each other.« less

Tuning carrier mobility without spin transport degrading in copper-phthalocyanine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, S. W.; Wang, P.; Chen, B. B.

2015-07-27

We demonstrate more than one order of magnitude of carrier mobility tuning for the copper-phthalocyanine (CuPc) without spin transport degrading in organic spin valve devices. Depending on the preparation conditions, organic spin valves with the CuPc film mobility of 5.78 × 10{sup −3} and 1.11 × 10{sup −4} cm{sup 2}/V s are obtained for polycrystalline and amorphous CuPc, respectively. Strikingly, the spin diffusion lengths are almost the same regardless of their mobilities that are ∼50 times different, which is in sharp contrast with previous prediction. These findings directly support that the spin relaxation in CuPc is dominated by the spin-orbit coupling.

Non-covalent interaction between Cu-phthalocyanine and methanato borondifluoride derivatives in two different medium

NASA Astrophysics Data System (ADS)

Pal, Chiranjit; Chaudhuri, Tandrima; Chattopdhyay, Subrata; Banerjee, Manas

2017-04-01

This study sort out chemical physics of non-covalent interaction between Copper phthalocyanine (CuPC) with Methanato borondifluoride derivatives (MBDF) in chloroform and ethanol. Formation of isosbestic points indicated stable ground state equilibrium between CuPC and MBDF, association ability were more pronounced in less polar chloroform. Interesting overall parallel orientation of MBDF over CuPC in gas phase geometries indicated that fluorine centre of MBDF lying just above the Cu-centre of CuPC. Thus strong interaction between Cu(II)- and F- centre could not be overruled and was also established by NBO calculation. TDDFT along with FMO features and heat of reaction values clearly designated the existence of π-π interaction and effect of solvent polarity on that interaction.

Direct construction of diverse metallophthalocyanines by manifold substrates in a deep eutectic solvent

NASA Astrophysics Data System (ADS)

Shaabani, Ahmad; Hooshmand, Seyyed Emad; Afshari, Ronak; Shaabani, Shabnam; Ghasemi, Vahid; Atharnezhad, Mojtaba; Akbari, Masoud

2018-02-01

Direct access to a wide range of metal-free phthalocyanines and metallophthalocyanines in deep eutectic solvents (DESs), is reported. Substituted and unsubstituted phthalocyanines of Mn, Fe, Co, Ni, Cu, Zn, Pd, In, and Pt with various raw materials such as phthalonitriles, phthalimides, phthalic anhydrides and phthalic acids are successfully prepared in the DES based on choline chloride and urea in a very short reaction time with appropriate yields. It has been shown that DES as a green and rapidly degraded reaction medium in the environment plays a triple role as a solvent, organocatalyst, and reactant in this process. Moreover, the DES system could be separated and reused in four consecutive reaction runs with no considerable loss in catalytic activity.

In vivo and in vitro absorption spectrum of disulphonated aluminum phthalocyanine in tumor-bearing mice

NASA Astrophysics Data System (ADS)

Cubeddu, Rinaldo; Canti, Gianfranco L.; Pifferi, Antonio; Taroni, Paola; Valentini, Gianluca

1995-03-01

The absorption spectrum of disulphonated aluminum phthalocyanine (AlS2Pc) between 650 nm and 695 nm was measured in vivo by means of time-resolved reflectance. The experiments were performed on mice bearing the L1210 leukemia 1, 4, and 7 hr after the i.p. administration of 2.5 mg/kg body weight (b.w.) of AlS2Pc. The absorption peak is centered at 685 nm, red-shifted of 10 - 15 nm with respect to the spectra obtained in solution in various environments. Measurements performed in vitro confirm the results in vivo and seem to suggest that the extracellular environment can cause the shift in the absorption line shape.

Artificial photosynthetic systems: assemblies of slipped cofacial porphyrins and phthalocyanines showing strong electronic coupling.

PubMed

Satake, Akiharu; Kobuke, Yoshiaki

2007-06-07

This paper reviews selected types of structurally well defined assemblies of porphyrins and phthalocyanines with strong electronic coupling. Face-to-face, head-to-tail, slipped cofacial, and non-parallel dimeric motifs constructed by covalent and non-covalent bonds are compared in the earlier sections. Their molecular orientation, electronic overlap, and absorption and fluorescence properties are discussed with a view towards the development of artificial photosynthetic systems and molecular electronics. Complementary coordination dimers are fully satisfactory in terms of structural stability, orientation factor, pi-electronic overlap, and zero fluorescence quenching. In later sections, several polymeric and macrocyclic porphyrin assemblies constructed by a combination of covalent bonds and complementary coordination bonds are discussed from the viewpoint of light-harvesting antenna functions.

Passivation of surface states in the ZnO nanowire with thermally evaporated copper phthalocyanine for hybrid photodetectors.

PubMed

Chen, Qi; Ding, Huaiyi; Wu, Yukun; Sui, Mengqiao; Lu, Wei; Wang, Bing; Su, Wenming; Cui, Zheng; Chen, Liwei

2013-05-21

The adsorption of O2/H2O molecules on the ZnO nanowire (NW) surface results in the long lifetime of photo-generated carriers and thus benefits ZnO NW-based ultraviolet photodetectors by suppressing the dark current and improving the photocurrent gain, but the slow adsorption process also leads to slow detector response time. Here we show that a thermally evaporated copper phthalocyanine film is effective in passivating surface trap states of ZnO NWs. As a result, the organic/inorganic hybrid photodetector devices exhibit simultaneously improved photosensitivity and response time. This work suggests that it could be an effective way in interfacial passivation using organic/inorganic hybrid structures.

Latent fingermark visualisation using reduced-pressure sublimation of copper phthalocyanine.

PubMed

Williams, Geraint; ap Llwyd Dafydd, Hefin; Watts, Alun; McMurray, Neil

2011-01-30

The sublimation of copper phthalocyanine (CuPc) at a temperature of 400°C under conditions of reduced pressure is shown to be an effective method of developing latent fingermarks on certain types of surface. Preliminary experiments on a limited selection of surfaces including paper, plastic and ceramic tiles were carried out using a simple apparatus consisting of a vacuum desiccator and a resistive heater. CuPc from the gas phase condenses preferentially on fingermark deposits, revealing deep blue patterns with excellent ridge detail clarity on light coloured surfaces. The technique is shown to be most effective on porous surfaces such as paper, but relatively ineffective on non-porous ceramic and plastic surfaces. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Carrier induced magnetic coupling transitions in phthalocyanine-based organometallic sheet.

PubMed

Zhou, Jian; Sun, Qiang

2014-01-07

A two-dimensional sheet with long range ferromagnetic (FM) order has been hotly pursued currently. The recent success in synthesizing polymerized Fe-phthalocyanine (poly-FePc) porous sheets paves a possible way to achieve this goal. However, the poly-FePc and its analog poly-CrPc structure are intrinsically antiferromagnetic (AFM). Using first principles combined with Monte-Carlo simulations, we study systematically the carrier-induced magnetic coupling transitions in poly-CrPc and poly-FePc sheets. We show that electron doping can induce stable FM states with Curie temperatures of 130-140 K, while hole doping will enhance the stability of the AFM states. Such changes in magnetic couplings depend on the balance of AFM superexchange and FM p-d exchange.

Optical limiting properties of optically active phthalocyanine derivatives

NASA Astrophysics Data System (ADS)

Wang, Peng; Zhang, Shuang; Wu, Peiji; Ye, Cheng; Liu, Hongwei; Xi, Fu

2001-06-01

The optical limiting properties of four optically active phthalocyanine derivatives in chloroform solutions and epoxy resin thin plates were measured at 532 nm with 10 ns pulses. The excited state absorption cross-section σex and refractive-index cross-section σr were determined with the Z-scan technique. These chromophores possess larger σex than the ground state absorption cross-section σ0, indicating that they are the potential materials for reverse saturable absorption (RSA). The negative σr values of these chromophores add to the thermal contribution, producing a larger defocusing effect, which may be helpful in further enhancing their optical limiting performance. The optical limiting responses of the thin plate samples are stronger than those of the chloroform solutions.

Coherent coupling between Vanadyl Phthalocyanine spin ensemble and microwave photons: towards integration of molecular spin qubits into quantum circuits.

PubMed

Bonizzoni, C; Ghirri, A; Atzori, M; Sorace, L; Sessoli, R; Affronte, M

2017-10-12

Electron spins are ideal two-level systems that may couple with microwave photons so that, under specific conditions, coherent spin-photon states can be realized. This represents a fundamental step for the transfer and the manipulation of quantum information. Along with spin impurities in solids, molecular spins in concentrated phases have recently shown coherent dynamics under microwave stimuli. Here we show that it is possible to obtain high cooperativity regime between a molecular Vanadyl Phthalocyanine (VOPc) spin ensemble and a high quality factor superconducting YBa 2 Cu 3 O 7 (YBCO) coplanar resonator at 0.5 K. This demonstrates that molecular spin centers can be successfully integrated in hybrid quantum devices.

Functional Nanomaterial’s Synthesis and Characterization

DTIC Science & Technology

2015-04-28

synthesis and characterization of nanoparticles and polymers. Current progress is being made at Argonne National Labs (ANL) and at AFRL in characterization... currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. Florida A&M University 1700 Lee Hall Drive 400 Foote-Hilyer Admin...at Florida A&M University (FAMU) which will play a key role in synthesis and characterization of nanoparticles and polymers. Current progress is

One-step preparation of a water-soluble carbon nanohorn/phthalocyanine hybrid for dual-modality photothermal and photodynamic therapy.

PubMed

Jiang, Bang-Ping; Hu, Lan-Fang; Shen, Xing-Can; Ji, Shi-Chen; Shi, Zujin; Liu, Chan-Juan; Zhang, Li; Liang, Hong

2014-10-22

The biomedical applications of carbon nanomaterials, especially integrating noninvasive photothermal therapy (PTT) and photodynamic therapy (PDT), into a single system have enormous potential in cancer therapy. Herein, we present a novel and facile one-step method for the preparation of water-soluble single-walled carbon nanohorns (SWNHs) and metal phthalocyanines (MPc) hybrid for PTT and PDT. The hydrophilic MPc, tetrasulfonic acid tetrasodium salt copper phthalocyanine (TSCuPc), is coated on the surface of SWNHs via noncovalent π-π interaction using the sonication method. In this PTT/PDT nanosystem, SWNHs acts as a photosensitizer carrier and PTT agent, while TSCuPc acts as a hydrophilic and PDT agent. The EPR results demonstrated that the generated reactive oxygen species (ROS) not only from the photoinduced electron transfer process from TSCuPc to SWNHs but also from SWNHs without exciting TSCuPc to its excited state. The test of photothermal conversion proved that not only do SWNHs contribute to the photothermal therapy (PTT) effect, TSCuPc probably also contributes to that when it coats on the surface of SWNHs upon exposure to a 650-nm laser. More importantly, the results of in vitro cell viability revealed a significantly enhanced anticancer efficacy of combined noninvasive PTT/PDT, indicating that the SWNHs-TSCuPc nanohybrid is a hopeful candidate material for developing an efficient and biocompatible nanoplatform for biomedical application.