Search

Abstract Coupling photosensitizers (PSs) with plasmonic nanoparticles increases the photocatalytic activity of PSs as the localized surface plasmon resonance (LSPR) of plasmonic nanoparticles leads to extreme concentration of light in their vicinity known as the near‐field enhancement effect. To realize this in a colloidal phase, efficient conjugation of the PS molecules with the plasmonic nanoparticle surface is critical. In this work, we demonstrate the coupling of phthalocyanine (Pc) molecules with gold nanoparticles (AuNPs) in the colloidal phase via click chemistry. This conjugated Pc‐AuNPs colloidal system is shown to enhance the photocatalytic singlet oxygen (1O2) production over non‐conjugated Pcs and hence improve the photoelectrochemical detection of phenols. The plasmonic enhancement of the 1O2 generation by Pcs was clearly elucidated by complementary experimental and computational classical electromagnetic models. The dependence of plasmonic enhancement on the spectral position of the excitation laser wavelength and the absorbance of the Pc molecules with respect to the wavelength specific near‐field enhancement is clearly demonstrated. A high ∼ 8 times enhancement is obtained with green laser (532 nm) at the LSPR due to the maximum near‐field enhancement at the resonance wavelength.

A Sn(IV) meso-tetra(4-methylthiolphenyl) N-confused porphyrin (4-Sn) complex was prepared to facilitate a comparison of the photophysicochemical and singlet oxygen photosensitiser properties of a series of Sn(IV) complexes of meso-4-methylthiolphenyl-substituted porphyrin, corrole, chlorin, and N-confused porphyrin. 4-Sn has an unusually high singlet oxygen quantum (ΦΔ) yield of 0.88, markedly higher than the ΦΔ values of the other complexes in this series. A Thorlabs M660L4 LED (280 mW · cm−2) was used to study the photodynamic activity of Sn-4 against the MCF-7 cancer cell line through irradiation at 660 nm for 30 min. The IC50 value was calculated to be 1.4 (± 0.8) µM, markedly lower than the previously reported values for the rest of the series. Photodynamic antimicrobial activity was also determined against Staphylococcus aureus and Escherichia coli, and 4-Sn was found to deactivate both Gram-(+) and Gram-(−) bacteria despite the absence of cationic charges on the ligand structure.

A series of tetraarylchlorins with 3-methoxy-, 4-hydroxy- and 3-methoxy-4-hydroxyphenyl meso-aryl rings (1-3-Chl) and their Sn(IV) complexes (1-3-SnChl) were synthesized and characterized so that their potential utility as photosensitizer dyes for use in photodynamic therapy (PDT) and photodynamic antimicrobial chemotherapy (PACT) can be assessed. The photophysicochemical properties of the dyes were assessed prior to in vitro PDT activity studies against MCF-7 breast cancer cells through irradiation with Thorlabs 625 or 660 nm LED for 20 min (240 or 280 mW·cm−2). PACT activity studies were performed against both planktonic bacteria and biofilms of Gram-(+) S. aureus and Gram-(−) E. coli upon irradiation with Thorlabs 625 and 660 nm LEDs for 75 min. The heavy atom effect of the Sn(IV) ion results in relatively high singlet oxygen quantum yield values of 0.69−0.71 for 1-3-SnChl. Relatively low IC50 values between 1.1−4.1 and 3.8−9.4 µM were obtained for the 1-3-SnChl series with the Thorlabs 660 and 625 nm LEDs, respectively, during the PDT activity studies. 1-3-SnChl were also found to exhibit significant PACT activity against planktonic S. aureus and E. coli with Log10 reduction values of 7.65 and >3.0, respectively. The results demonstrate that the Sn(IV) complexes of tetraarylchlorins merit further in depth study as photosensitizers in biomedical applications.

Integration of adsorption and photocatalysis processes can lead to several benefits in water treatment. Integrating well-known adsorbents with photocatalysts ensures that all the interesting components are preserved and helps to overcome the serious downsides of each material and technique when operated independently. In this work, we introduce a new concept of combining both absorption and photodegradation mechanisms using organic photocatalytic adsorbents for water purification. This was achieved by formulating photosensitizing hybrids based on a newly synthesized chloroindium (III) 5,10,15,20-tetrakis(4-acetamidophenyl) porphyrin (InTAAP) compound, anchored on oxygen functionalized coconut shell-based activated carbon granules supports. The fashioned integrated photocatalyst adsorbent hybrid (InTAAP(ACO)) was then studied for their adsorption and photodegradation efficiency using methylene blue dye, where InTAAP(ACO) showed excellent photocatalytic activity compared to ACO and unfunctionalized activated carbon granules (AC), with appreciably high and adsorption properties as AC and ACO.

Abstract A novel observation of the formation of carbon wire in a carbon-based liquid solvent, using in liquid high voltage AC arc discharge is described. The authors describe the observed phenomenon, technical equipment needed to achieve the effect and preliminary qualitative results of obtained material. The wire consisted of well packed layers of carbon elements. The arc-discharge method is a simple, low cost method for the production of three dimensional carbon structures. A further research is needed to get a thorough understanding of the phenomenon.

A method is presented for the electrochemical detection of the breast cancer biomarker human epidermal growth factor receptor 2 (HER2). A glassy carbon electrode was modified using two techniques known as sequential adsorption and electro-polymerization, and the results are compared. The highly conductive polypyrrole (PPy) is used, in the presence of sulfur/nitrogen doped graphene quantum dots (SNGQDs) and a known cobalt phthalocyanine (CoPc). The different nanomaterials were used as an immobilization platform for the HER2 specific HB5 aptamer via amide linkage. The nanomaterials were arranged in various ways on the glassy carbon electrode, to investigate the effect of the electrode interface on the operational characteristics of a biosensor. The immobilized aptamer selectively recognizes HER2 on the electrode interface, and this leads to an increased charge transfer resistance (Rct) of the electrode when using ferricyanide as the electrochemical probe. The developed immunosensors showed high sensitivity with the best detection limit of 0.00141 ng/mL. The results showed that the method is simple and sensitive enough for the determination of HER2 in serum samples with good reproducibility and accuracy.

Human papillomavirus (HPV) DNA detection can enable the early diagnosis of high-risk HPV types responsible for cervical cancer. HPV detection is also essential for investigating the clinical behavior and epidemiology of particular HPV types, characterization of study populations in HPV vaccination trials and monitoring the efficacy of HPV vaccines. In this study, two azaBODIPY dyes (1 and 2) were used as references and were doped into polystyrene particles (PS40), while a short HPV DNA single strand was used as a target molecule and was covalently bound to the silica shell. These particles were employed as optical probes in 1:1 hybridization assays, and their potential applicability as a tool for multiplex assays for the detection of different strands of HPV was evaluated using flow cytometry. A good separation in the fluorescence of the four different concentrations prepared for each dye was observed. To perform the hybridization assays, HPV18, HPV16, HPV11 and HPV6 single strands were attached to the particles through EDC-mediated coupling. The c-DNA-1-PS40 and c-DNA-2-PS40 particles exhibited low limit of detection (LOD) and quantification (LOQ) values for HPV11, and a narrow detection range was obtained. Multiplexed assay experiments were successfully performed for both particles, and the results proved that c-DNA-1-PS40 could potentially be used as a tool for multiplexing assays and merits further in-depth study in this context.

N4 macrocyclic complexes of Al and Zn phthalocyanines with symmetrical imine and imidazole moiety at the periphery were synthesized. The synthesized ligands, complexes, and polymers were purified and characterized to study the structure of the molecule. These synthesized complexes were used for photodynamic therapy application as the diamagnetic Zn and Al have the ability to produce and stabilize singlet oxygen species. The synthesized N4 molecules of aluminum iminomethoxy phenyl phthalocyanine and aluminum ethyl phenyl benzimidazolephthalocyanine showed better activity against MCF-7 cells. These results suggest that this assay may be used as an early biomarker of clinical response.

Plasmonic gold nanoparticles significantly improved the efficiency of a TiO2 and Eosin Y based dye-sensitized solar cell from 2.4 to 6.43%. The gold nanoparticles’ sizes that were tested were 14 nm, 30 nm and 40 nm synthesized via the systematic reduction of citrate concentration using the Turkevich method. Prestine TiO2 without plasmonic gold nanoparticles yielded an efficiency of 2.4%. However, the loading of 40 nm gold nanoparticles into the TiO2 matrix yielded the highest DSSC efficiency of 6.43% compared to 30 nm (5.91%) and 14 nm (2.6%). The relatively high efficiency demonstrated by plasmonic gold nanoparticles is ascribed to light absorption/scattering, hot electron injection and plasmon-induced resonance energy transfer (PIRET), influenced by the size of the gold nanoparticles.

New asymmetrical porphyrin derivatives containing a p-hydroxyphenyl moiety and p-acetylphenyl moieties along with their functionalized silver-detonation nanodiamonds nanohybrids were characterized and their photophysicochemical properties were established. The study provides evidence that the metalated porphyrin derivatives were red-shifted in absorption wavelength and possessed high singlet oxygen quantum yield comparative to the unmetalated core, thus making them suitable agents for photodynamic antimicrobial chemotherapy. As a result of conjugation to detonation nanodiamonds and silver nanoparticles, these compounds proved to be more effective as they exhibited stronger antibacterial and anti-biofilm activities on the multi-drug resistant S. aureus strain due to synergetic effect, compared to Ps alone. This suggests that the newly prepared nanohybrids could be used as a potential antimicrobial agent in the treatment of biofilms caused by S. aureus strain.

Tetrakis[(benzo[d]thiazol-2-yl-thio) phthalocyaninato] gallium(III)chloride (1) and tetrakis[(benzo[d]thiazol-2ylphenoxy) phthalocyaninato] gallium(III)chloride (2) were successfully electrodeposited onto aluminium for corrosion retardation in 1.0 M hydrochloric acid solution. The aim of this study was to compare the corrosion resistance of electrodeposited metallated phthalocyanines. Scanning electron microscopy, X-ray diffraction, electrochemical impedance spectroscopy (EIS), and polarization confirmed the aluminium corrosion inhibition potentials of complexes 1 and 2. EIS and polarization techniques showed that complex 2 performed better than complex 1, with values from EIS measurements of 82% for 1 and 86% for 2 in 1.0 M hydrochloric acid solution. The importance of electrodeposition in industries and a dearth of research on the use of electrodeposited metallated phthalocyanines necessitated this study, and results show that coatings formed by electrodeposition of 1 and 2 onto aluminium reduced its susceptibility to corrosion attack.

The synthesis and characterization of A3B-type phthalocyanines, ZnPc1–4, bearing bulky 2,6-diisopropylphenoxy-groups or chlorine atoms on isoindoline units “A” and either one or two carboxylic anchors on isoindoline unit “B” are reported. A comparison of molecular modelling with the conventional time dependent—density functional theory (TD-DFT) approach and its simplified sTD-DFT approximation provides further evidence that the latter method accurately reproduces the key trends in the spectral properties, providing colossal savings in computer time for quite large molecules. This demonstrates that it is a valuable tool for guiding the rational design of new phthalocyanines for practical applications.

Abstract Over centuries, the external factors such as fire, low temperature, light or microbiological agents, act on the wood and induce some degradation processes, sometimes irreversible, identified by discoloration, fragility and unsightly appearance. Although there are numerous literature reports about different nanomaterials used for preservation and restoration of wood surfaces (calcium hydroxides, magnesium hydroxides, hydroxyapatite, or even organic resins as Paraloid B72), in this paper it is proposed a new system—gold hydroxyapatite (AuHAp), tested on the hazelnut wood samples (young and aged specimens), as a new solution for preservation of some wooden artifacts. This paper addresses a broad range of analytical methods: X-ray diffraction, UV–Vis spectrophotometry, Fourier transformed infrared spectroscopy, Raman spectroscopy, scanning electron microscopy with energy dispersive spectroscopy, chromatic parameters and hardness test. Also, humidity sorption/desorption measurements are used for humidity sorption and desorption evaluation. The adsorption and desorption tests determined the hydroscopic sorption properties of the wood specimens by measuring the mass of the specimens in equilibrium with air at a specific temperature and RH. All the results concluded that after the application of the new system on the hazelnut wood surface, a well distributed and uniform layer consisting from AuHAp systems with a network aspect are observed, which covers the wood vessels and fibers, filling the voids and stopping the wood weathering process, more accentuated at aged wood than at the young species.

The absence of a secure long-term sustainable energy supply is recognized as a major worldwide technological challenge. The generation of H2 through photocatalysis is an environmentally friendly alternative that can help solve the energy problem. Thus, the development of semiconductor materials that can absorb solar light is an attractive approach. TiO2 has a wide bandgap that suffers from no activity in the visible spectrum, limiting its use of solar radiation. In this research, the semiconductor absorption profile was extended into the visible region of the solar spectrum by preparing porphyrin-TiO2 (P-TiO2) composites of meso-tetra(4-bromophenyl)porphyrin (PP1) and meso-tetra(5-bromo-2-thienyl)porphyrin (PP2) and their In(III), Zn(II) and Ga(III) metal complexes. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were performed on the porphyrins to gain insight into their electron injection capability. The results demonstrate that P-TiO2 systems merit further in-depth study for applications that require efficient photocatalytic H2 generation.

The optical limiting (OL) properties of a 3,5-di-p-benzyloxystyrylBODIPY dye with an p-acetamidophenyl moiety at the meso-position have been investigated by using the open-aperture Z-scan technique at 532 nm with 10 ns laser pulses. There is a ca. 140 nm red shift of the main spectral band to 644 nm relative to the corresponding BODIPY core dye, due to the incorporation of p-benzyloxystyryl groups at the 3,5-positions. As a result, there is relatively weak absorbance across most of the visible region under ambient light conditions. Analysis of the observed reverse saturable absorbance (RSA) profiles demonstrates that the dye is potentially suitable for use in optical limiting applications as has been reported previously for other 3,5-distyrylBODIPY dyes. Time-resolved transient absorption spectroscopy and kinetic studies with femtosecond and nanosecond scale laser pulses provide the first direct spectral evidence that excited state absorption (ESA) from the S1 state is responsible for the observed OL properties.

ClIn(III) octacarboxy phthalocyanine (ClInOCPc) when alone or conjugated to magnetic nanoparticles (MNP-ClInOCPc) was employed for both photodynamic antimicrobial chemotherapy of an unknown water sample and Staphylococcus aureus, and for photo-degradation of methyl red (MR). The singlet oxygen quantum yields (ΦΔ) in water using ClInOCPc and MNP-ClInOCPc embedded in polyacrylonitrile (PAN) electrospun fibers were 0.36 and 0.22, respectively. When in solution, MNP-ClInOCPc gave 90.6% photoinactivation of microbes in a water sample from the stream and of ClInOCPc resulted in 84.8 % photoinactivation. When embedded to the polymer, there was 48.0% clearance for ClInOCPc and 63.7% clearance for MNP-ClInOCPc for the microbes in the water sample from the stream. For the photo-degradation of MR, the rate of degradation increased with decrease of the MR concentration with the MNP-ClInOCPc having the fastest rate.

Bifunctional nanocomposites based on zinc phthalocyanines and glutathione capped CoFe2O4 magnetic nanoparticles (GSH-CoFe2O4 MNPs) are applied in a binary system wherein simultaneous photooxidation of methyl orange (MO) and photoreduction of Cr (VI) are conducted. The photoactivity of two zinc Pcs with different functional moieties are compared based on their interactions with GSH-CoFe2O4 MNPs. Conjugation of the Pcs to the GSH-CoFe2O4 MNPs not only enhanced their singlet oxygen production but also their photocatalytic activity in both photooxidation and photoreduction experiments. Using electron paramagnetic resonance (EPR) spectroscopy, the Pc-MNP conjugates reported herein were found to exhibit superparamagnetic behaviour, giving the advantage of easy separation using an external magnetic field post application, an attractive attribute for heterogeneous catalysis. The catalysts reported herein are therefore good candidates as catalysts for real life water purification analyses as they facilitate the treatment of both organic and inorganic water pollutants.

Two near-infrared (NIR) absorbing di(thien-2-nyl)-di(dimethylanilino)azaBODIPY dyes 2a and 2b were synthesized and characterized that differ depending on whether the dimethylaniline substituents are introduced at the 3,5- or 1,7-positions of the azaBODIPY core. The main spectral bands lie at 824 and 790 nm, respectively, in CH2Cl2. The effect of substituent position on the photophysical and pH sensing properties was analyzed through a comparison of the optical properties with the results of time-dependent density functional theory (TD-DFT) calculations. Protonation of the dimethylamino nitrogen atoms eliminates the intramolecular charge transfer properties of these compounds, and this results in a marked blue-shift of the main absorption bands to 696 and 730 nm, respectively, in CH2Cl2, and a fluorescence “turn-on” effect in the NIR region. The pH dependence studies reveal that the pKa values of the non-protonated 2a and 2b molecules are ca. 6.9 (±0.05) and 7.3 (±0.05), respectively, while that of the monoprotonated species for both dyes is ca. 1.4 (±0.05) making them potentially suitable for use as colorimetric pH indicators under highly acidic conditions.

This study describes the adsorption behavior of organic inhibitors at the aluminum-HCl solution interface and their corrosion inhibition performance. The organic inhibitors employed are: 4-(benzo [d]thiazol-2ylthio)phthalonitrile (BTThio) and tetrakis[(benzo[d]thiazol-2-yl-thio)phthalo- cyaninato]gallium(III) chloride (ClGaBTThioPc). The corrosion behavior of these inhibitors is investigated using electrochemical and computational techniques. Open circuit potential results reveal predominant cathodic character for the mechanism of aluminum corrosion inhibition by the inhibitors. Inhibition efficiency values from potentiodynamic polarization measurements increase from 46.9 to 70.8% for BTThio and 59.7 to 81.0% for ClGaBTThioPc within the concentration range of 2 to 10 μM. Scanning electron microscopy (SEM) measurements reveal protection of the metal surface from acid attack, in the presence of the inhibitors and energy dispersive X-ray (EDX) measurements show that the most probable way by which the inhibitors protect the metal surface would be by shielding it from the corrosion attacks of Cl− from the acid. Quantum chemical parameters corroborate well with experimental findings.

The purpose of this review is to compile preclinical and clinical results on phthalocyanines (Pcs) as photosensitizers (PS) for Photodynamic Therapy (PDT) and contrast agents for fluorescence imaging. Indeed, Pcs are excellent candidates in these fields due to their strong absorbance in the NIR region and high chemical and photo-stability. In particular, this is mostly relevant for their in vivo activation in deeper tissular regions. However, most Pcs present two major limitations, i.e., a strong tendency to aggregate and a low water-solubility. In order to overcome these issues, both chemical tuning and pharmaceutical formulation combined with tumor targeting strategies were applied. These aspects will be developed in this review for the most extensively studied Pcs during the last 25 years, i.e., aluminium-, zinc- and silicon-based Pcs.

It is shown that iron(II) tetra-aminophthalocyanine complex electropolymerized onto a multi-walled carbon nanotube-modified basal plane pyrolytic graphite electrode greatly enhanced the electrocatalytic detetion of amitrole (a toxic herbicide), resulting in a very low detection limit (0.5 nM) and excellent sensitivity of 8.80±0.44 μA/nM, compared to any known work reported so far. The electrocatalytic detection of amitrole at this electrode occurred at less positive potential (~0.3 V vs Ag|ACl) and also revealed a typical coupled chemical reaction. The mechanism for this response is proposed. The electrode gave satisfactory selectivity to amitrole in the presence of other potential interfering pesticides in aqueous solutions.