Encapsulation of zinc phthalocyanine into bovine serum albumin aggregates

Artificial hybridization of molecules with proteins is beneficial for biomedical applications. Herein, we describe a novel method for encapsulation of zinc phthalocyanine (ZnPc) aggregates into bovine serum albumin (BSA) aggregates, but not monomeric BSA. This property is potentially useful for not only photodynamic or photothermal therapy but also development of a novel delivery system for hydrophobic drug molecules.     

Study of fluorescent aggregates of polymethine dyes

Absorption, fluorescence, and fluorescence excitation spectra have been studied for a number of anionic, cationic, and cationic-anionic polymethine dyes in low-polar and nonpolar solvents, as well as in binary mixtures of solvents differing in polarity. For most of the dyes studied, fluorescent aggregates have been found to form. Their broad fluorescence bands are located in the long-wave region with respect to those of the initial dyes. The quantum yield of the aggregate fluorescence is normally higher than that of the initial dyes. Fluorescence excitation spectra of some cationic-anionic dyes in nonpolar solvents disagree with their absorption spectra because of contact and solvent-separated ion pairs simultaneously present in the solution.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 69–75, January, 1993.     

The first stable mononuclear silyl palladium hydrides

The reaction of tertiary silanes with the low valent palladium complex [(mu-dcpe)Pd]2 affords equilibrium mixtures with mononuclear silyl palladium hydrides. These complexes have been characterized by NMR spectroscopy and, in one case, by X-ray crystallography. The silyl palladium hydride complexes rapidly interchange silicon and hydride coordination environments in solution which give rise to extraordinary temperature-dependent kinetic isotope effects for the fluxional process. An intermediate 2eta-Si-H complex is proposed for the interchange.     

Observation of a fluorescent dimer of a sulfonated phthalocyanine

With very few exceptions, phthalocyanine dimers are found to be nonfluorescent. We report here the observation of a fluorescent dimer of a tetrasulfonated copper phthalocyanine in ethanol and water. Fluorescence excitation and emission spectra at room temperature and at 77 K are presented. These are consistent with the conventional model of exciton coupling in a cofacial dimer.     

Time resolved observation of geminate recombination in metal-free phthalocyanine

Delayed-collection-field measurements of carrier generation and delayed fluorescence in metal-free phthalocyanine have been shown to exhibit the same time dependence. This indicates the existence of geminate electron—hole pairs with survival times extending to tens of milliseconds.     

Characterization of fluorescent surfactant aggregates by fluorimetric and viscosimetric techniques

Summary A combination of fluorimetric and viscosimetric methods was used to characterize N,N-dimethyl-N-2-(4-(t-butylphenoxy)ethoxy)ethyl-N-hexadecylammonium chloride (BDHC), a doubletailed surfactant with dissimilar tail groups.BDHC was observed to fluoresce at 315 nm when excited at 274 nm, a feature which could be utilized to determine its critical micelle concentration (CMC). A value of 3.98×10^–5 M was obtained and was observed to be slightly temperature dependent with aT _min of 25.35°C. Fluorescence quenching experiments using 4-nitroaniline as a quencher were performed in order to determine the aggregation number which was found to be 42.0. The hydrodynamic radius of 21.91 Å was obtained using data from viscosimetric experiments. These data, together with theTanford andEinstein-Stokes relationships, were used to determine the micellar structure (spherical) and the diffusion coefficient (D=0.97×10^–6 cm²/s), respectively. The G of micellization forBDHC was determined to be –34.9 kJ/mol.

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Charakterisierung fluoreszierender oberflächenaktiver Aggregate mittels Fluorimetrie und Viskosimetrie

Zusammenfassung Die Verbindung N,N-Dimethyl-N-2-(4-(t-butylphenoxy)ethoxy)ethyl-N-hexadecylammoniumchlorid (BDHC), eine oberflächenaktive Substanz mit zwei unterschiedlichen Seitenketten, wurde mittels einer Kombination von fluorimetrischen und viskosimetrischen Methoden charakterisiert. Anregung bei 274 nm ruft eine Fluoreszenz bei 315 nm hervor; diese Eigenschaft wurde zur Bestimmung der kritischen Micellenkonzentration (CMC) herangezogen. Es wurde ein geringfügig temperaturabhängiger Wert von 3.98×10^–5 M gefunden (T _min=25.35°C). Quenchexperimente mit 4-Nitroanilin ergaben eine Aggregationszahl von 42.0, viskosimetrische Untersuchungen einen hydrodynamischen Radius von 21.91 Å. Die erhaltenen Daten erlauben zusammen mit den Beziehungen nachTanford undEinstein-Stokes die Bestimmung der Micellenstruktur (sphärisch) und des Diffusionskoeffizienten (0.97×10^–6 cm²/s). Das G der Micellenbildung fürBDHC beträgt –34.9 kJ/mol.

     

Preparation and characterization of first optically active rigid phthalocyanine dimers

The first optically active rigid covalently linked by enantiomerically pure (R)- or (S)-BINOL metal-free phthalocyanine dimers have been prepared and characterized using electronic absorption, CD, MCD, MS, and NMR techniques as well as semi-empirical molecular orbital calculations.     

Observation of zinc phthalocyanine aggregates on a water surface using grazing incidence X-ray scattering

Reported here are the structural properties of a zinc 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine Langmuir monolayer on a water surface under progressive lateral compression investigated by grazing incidence X-ray scattering. Grazing incidence diffuse X-ray scattering out of the specular plane (GIXOS) is exploited to determine specular reflectivity-like information where the phase change of flat-lying molecules on the surface to edge-standing molecules perpendicular to the surface is directly observed. Furthermore, grazing incident X-ray diffraction (GIXD) is used to investigate the in-plane ordering of the system where it has been found that in the high-density state (approximately 0.35 nm2 per molecule) the system can be considered to be a monolayer consisting of arrays of side-by-side lying cofacially aggregated cylindrical rodlike entities.     

A pH-responsive fluorescent probe and photosensitiser based on a self-quenched phthalocyanine dimer

A self-quenched zinc(ii) phthalocyanine dimer linked with an acid-sensitive ketal unit has been prepared, which can be activated in an acidic environment (pH = 5.0-6.5) as a result of the cleavage of the ketal linker and separation of the phthalocyanine units, resulting in enhanced fluorescence emission and singlet oxygen production.     

Structural characterisation of the first mononuclear bismuth porphyrin

A single carboxylate picket bismuth porphyrin has been characterised in the solid state as the first instance of a non-dimeric structure; the carboxylate picket, bent over the macrocycle, is coordinated to the bismuth, inducing a significant distortion of the porphyrin core.     

酞菁和酞菁铜的三阶非线性光学性质

用INDO/SDCI方法研究了酞菁和酞菁铜的电子结构, 紫外-可见光谱, 三阶非线性光学系数及其色散效应, 发现酞菁铜中Cu^2+对γ的贡献很小, 故酞菁与酞菁铜的γ几乎相等, 我们的计算结果对此进行了合理的解释。     

The first ESR observation of radical species in subcritical water

Triphenylmethanol was treated in subcritical and supercritical water. A radical species, triphenylmethyl radical, was directly generated from triphenylmethanol in subcritical and supercritical water without using any radical initiator. The radical formation was confirmed by direct electron spin resonance (ESR) measurement in high-temperature and high-pressure subcritical water and by capturing the radical intermediate using hydrogen donors in supercritical water.     

Berberine alkaloid as a sensitive fluorescent probe for bile salt aggregates

Effect of sodium cholate (NaC) bile salt on the absorption and fluorescence properties of berberine cation was studied in aqueous solution and water-cosolvent mixtures. The alteration of the fluorescent behavior with increasing NaC concentration showed an entirely different trend from that found previously in the presence of sodium dodecylsulfate. Binding to bile salt agglomerates led to significant fluorescence intensity enhancement, and the fluorescence lifetime of berberine proved to be highly sensitive to the structure and size of the aggregates. The dual exponential decay kinetics above 10 mM NaC concentration showed that the probe resided in two totally different binding sites. At 2-10 mM NaC concentrations, only primary aggregates were detected. The aggregate disrupting power of cosolvents decreased in the series of dimethylformamide, acetonitrile, formamide, and methanol. These compounds enhanced the water accessibility of berberine bound to aggregates and diminished the number of secondary aggregates.     

Understanding the factors governing the water oxidation reaction pathway of mononuclear and binuclear cobalt phthalocyanine catalysts

The rational design of efficient catalysts for electrochemical water oxidation highly depends on the understanding of reaction pathways, which still remains a challenge. Herein, mononuclear and binuclear cobalt phthalocyanine (mono-CoPc and bi-CoPc) with a well-defined molecular structure are selected as model electrocatalysts to study the water oxidation mechanism. We found that bi-CoPc on a carbon support (bi-CoPc/carbon) shows an overpotential of 357 mV at 10 mA cm⁻², much lower than that of mono-CoPc/carbon (>450 mV). Kinetic analysis reveals that the rate-determining step (RDS) of the oxygen evolution reaction (OER) over both electrocatalysts is a nucleophilic attack process involving a hydroxy anion (OH⁻). However, the substrate nucleophilically attacked by OH⁻ for bi-CoPc is the phthalocyanine cation-radical species (Co^II–Pc–Pc˙⁺–Co^II–OH) that is formed from the oxidation of the phthalocyanine ring, while cobalt oxidized species (Pc–Co^III–OH) is involved in mono-CoPc as evidenced by the operando UV-vis spectroelectrochemistry technique. DFT calculations show that the reaction barrier for the nucleophilic attack of OH⁻ on Co^II–Pc–Pc˙⁺–Co^II–OH is 1.67 eV, lower than that of mono-CoPc with Pc–Co^III–OH nucleophilically attacked by OH⁻ (1.78 eV). The good agreement between the experimental and theoretical results suggests that bi-CoPc can effectively stabilize the accumulated oxidative charges in the phthalocyanine ring, and is thus bestowed with a higher OER performance.

bi-CoPc can stabilize accumulated oxidative charges in phthalocyanine ring, which leads to the OER proceeding through a nucleophilic attack of OH^- on the phthalocyanine cation-radical species that is formed from the oxidation of phthalocyanine ring.     

The photodegradation of a zinc phthalocyanine

A water-soluble zinc phthalocyanine (Pc), ZnPc (3), bearing 12 dimethylamino groups, which enhance the solubility of the macrocycle was synthesized and characterized. Photobleaching of the compound was examined both in vivo and in vitro. Laser irradiation causes photo-oxidation of the newly synthesized ZnPc. A photobleachable phthalocyanine can be an alternative in imaging; phthalocyanine dyes are used in imaging the cardiovascular system. Besides, it can be used in fluorescein angiography in some cases. When compared to stable ones, a photobleaching ZnPc (3) might be an attractive compound for imaging in medicine.     

The synthesis of a fluorinated phthalocyanine

The reaction of perfluoroalkylcopper with 4-iodophthalonitrile provides a convenient route to fluorinated phthalonitriles which readily form phthalocyanines in the presence of stannous chloride dihydrate.During the course of preparing 4-perfluoroheptylphthalonitrile $\text{1}$, a secondary reaction was observed when the reaction time was extended beyond two hours. This reaction involves the interaction of the orthodinitrile with copper and/or cuprous iodide to afford the phthalocyanine nucleus. This coaction is portrayed by the appearance of a green color in the reaction media.