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Antimicrobial resistance is a matter of concern to all biological systems. This work investigates the antimicrobial activity of porphyrins conjugated to pristine graphene quantum dots (pGQDs) through non-covalent linking. A novel In 5,10,15,20-tetrakis[4-(benzyloxy) phenyl] porphyrin (InTBnOPP) was synthesized and fully characterized. The photophysicochemical parameters of H2TBnOPP, ZnTBnOPP, InTBnOPP, and their conjugates were investigated. It was found that pGQDs improved the singlet oxygen quantum yield upon conjugation with the porphyrins. pGQDs-InTBnOPP had a higher singlet oxygen quantum yield of 0.80 when compared to all other conjugates. Porphyrins are well-known photosensitizers for photodynamic antimicrobial chemotherapy (PACT); this was also confirmed by pGQDs-ZnTBnOPP and pGQDs-InTBnOPP which completely inhibited both S. aureus and E. coli with log reduction values of 9.42 and 8.59 with an irradiated time of 5 and or 10 min, respectively. The porphyrins alone had significant antibacterial activities. In general, the obtained results demonstrate a good response of these nanoconjugates against Gram (+) and Gram (-) bacteria.

The development and advancement of electrospinning (ES) presents a unique material technology of the future achieved by fabricating novel nanofibrous materials with multifunctional physical (three-dimensional [3D] structure, nanoscalable sizes) and chemical characteristics (functional groups). Advancing the possibility of preparing various classes of novel organic and inorganic electrospun fiber composites with unique features such as polymer alloys, nanoparticles (NPs), active agents, and devices. This feature gives provision for internal access of the setup parameters such as polymer precursor material, polymer concentration, solvent, and the method of fiber collection that consequentially improves the intrinsic control of the construction mechanism of the final nanofibrous architecture. In synthetic electrospinning, the nanofibrous material processing allows for internal control of the electrospinning mechanism and foster chemical crosslinking to generate covalent connections between polymeric fibers. Comparing technologies according to materials of the future revealed that electrospinning supports the formation of micro-scale and in some cases nano-scale fibers while the formation of thin films is facilitated by the electrospraying system. Recent innovations point to various biomass waste streams that may be used as an alternative source of polymeric materials for application in electrospinning to produce materials for the future.

Zinc tetra morpholine porphyrin (complex 2), and its quaternized derivative (complex 3) were synthesized and conjugated to folic acid decorated nitrogen doped graphene quantum dots (FA-NGQDs) through π-π stacking to study their photodynamic therapy (PDT) efficacy. Photophysiochemical properties of complexes 2, 3, and their conjugates (2-FA-NGQDs, 3-FA-NGQDs) were studied. It was found that complex 3 had higher ϕ

The present work reports on the synthesis and characterization of novel zinc (2) and indium (3) 2-amino-4-bromophenoxy substituted phthalocyanines (Pcs) along with the self-assembled nanoconjugates formed via π–π stacking interaction onto detonation nanodiamonds (DNDs) to form 2@DNDs and 3@DNDs. 2@DNDs and 3@DNDs were covalently linked to chitosan–silver mediated nanoparticles (CSAg) to form 2@DNDs-CSAg and 3@DNDs-CSAg nanoconjugates. High singlet oxygen quantum yields in DMSO of 0.69 and 0.72 for Pcs alone and 0.90 and 0.92 for 2@DNDs-CSAg and 3@DNDs-CSAg, respectively, were obtained. The photodynamic antimicrobial chemotherapy (PACT) activity of both phthalocyanines and nanoconjugates was tested against planktonic cells and biofilms of S. aureus. 2@DNDs-CSAg and 3@DNDs-CSAg caused effective killing with a log reduction of 9.74. In addition, PACT studies on single-species S. aureus biofilms were carried out with log reduction values of 5.12 and 5.27 at 200 μg mL−1 for 2@DNDs-CSAg and 3@DNDs-CSAg, respectively.

Herein, we report on the development of an effective, environmentally benign and facile method for visible light driven photo-degradation of Rhodamine 6 G and 2,4-dichlorophenol using Zn-5-p-carboxyphenyl-10,15,20-(tris-4-pyridyl)-porphyrin (2) linked to graphitic carbon nitride quantum dots (g-C3N4 QDs) and anchored on TiO2 fibers (represented as 2@g-C3N4 QDs-TiO2 fibers). The results suggest that the porphyrin acts as a photosensitizer, g-C3N4 QDs function as both photosensitizer and electron mediator, whereas the TiO2 fibers supporting matrix is a photocatalyst and a stabilizer. Anchoring 2@g-C3N4 QDs onto TiO2 fibers resulted in enhanced catalytic activity and thermal stability. Singlet oxygen (1O2) was the main reactive species responsible for degradation of Rhodamine 6 G and 2,4-dichlorophenol. The degradation kinetic studies follow pseudo first-order kinetics. The results demonstrate 2@g-C3N4 QDs-TiO2 fibers ternary hybrid catalyst to be a catalyst for visible light driven photo-degradation of refractory organic water pollutants.

Novel asymmetric 5-(4-bromo)-10-15-20-tris-(4-morpholine)porphyrin (complex 1) and its Zn derivative (2) were synthesized, and the latter was quaternized to give 2Q, and their photodynamic therapy (PDT) activities were compared to those of the symmetric tetra-morpholine porphyrin (3) and its respective quaternized analogue (3Q). Respective porphyrins were further conjugated to biotin-nitrogen doped graphene quantum dots (B-NGQDs) through π-π stacking. It was observed that the asymmetric complexes and their conjugates had high singlet oxygen quantum yields when compared to the symmetrical porphyrin and their conjugates. PDT studies were performed using MCF-7 breast cancer line. It was observed that all the complexes/conjugates have negligible dark toxicity, and 2Q-B-NGQDs had a highest PDT efficiency with cell viability of 14.4% and IC50 of 1.41 µg/mL.

The syntheses and characterization of symmetric and asymmetric Pcs functionalized at the peripheral position and sometimes positively charged are reported. The Pcs had either H2, zinc or silicon as central metals and have pyridyloxy, benzothiozole phenoxy, and respective cationic analogues as ring substituents. The Pcs were linked to carbon based nanoparticles such as graphene quantum dots, carbon dots, and detonation nanodiamonds (DNDs) via an ester, amide bond and/or π - π stacking. The physicochemical characteristics of the Pcs were assessed when alone and when in a conjugated system. Both symmetrically and asymmetrically substituted benzothiozole Pcs when quaternised displayed higher triplet and singlet oxygen quantum yields than their unquaternised counterparts. Linkage to carbon nanoparticles (especially to detonation nanodiamonds) had an increasing effect on triplet and singlet oxygen quantum yield. However, a general decrease in singlet oxygen quantum yield on linkage to doped detonation nanodiamonds was associated with the screening effect of DNDs. Heteroatom doped DNDs-Pc nanohybrids have less singlet oxygen than Pcs alone due to molecular structural stability associated with strain that is relatively reduced upon linking Pcs. The In vitro dark cytotoxicity and photodynamic therapy of selected Pc complexes and conjugates against MCF-7 cells was tested. All studied Pc complexes and conjugates showed minimum dark toxicity making them applicable for PDT. When Pc complexes are alone, there is less phototoxicity with >22% cell viability at concentrations ≤ 50 μg/mL relative to conjugates with

The synthesis, photophysicochemical and photodynamic therapy (PDT) activities of benzothiazole substituted zinc phthalocyanine (Pc): 1 (asymmetrically substituted and composed of no charges), 2 (asymmetrically substituted and composed of three positive charges), and 3 (symmetrically substituted and composed of four positive charges), are presented. The triplet and singlet oxygen quantum yields were highest for complex 2 showing the importance of asymmetry and charge. The complexes are covalently and non-covalently linked to B doped detonation nanodiamonds (B@DNDs) to yield nanohybrids (B@DNDs-1, B@DNDs-2, B@DNDs-3). The presence of B@DNDs, asymmetry and positive charge resulted in improved PDT with the lowest cell viability being observed for B@DNDs-2 at 5%. The cell viability ranged from 5% to 7% for the nanohybrids compared to 19-26% for Pcs alone.

In this study photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-phthalocyanine nanoconjugate systems containing: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (H2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato zinc(II) (ZnTPPc) and 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyanato silicon(IV) hydroxide (Si(OH)2TPPc), were investigated in dimethylsulfoxide solution. Pcs were non-covalently linked to nanondiamonds (also covalently linked for Si(OH)2TPPc) and investigated using 532 nm laser excitation at 10 ns pulses for their optical limiting properties. Complexes that have higher triplet state absorption also possessed enhanced nonlinear optical behaviour following reverse saturable absorption mechanism. Superior optical performance is observed when the Pcs had a central metal with axial ligands conjugated to DNDs in solution. Nanoconjugate of DNDs-Si(OH)2TPPc and respective Pc in solution gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability (γ) at 2.91 × 10−8 and 3.17 × 10−8 esu and 3.88 × 10−28 and 4.22 × 10−28 esu, respectively, with Ilim value of 0.47 and 0.39 J·cm−2.

The synthesis, photophysicochemical and photodynamic therapy (PDT) activity of quaternary benzothiazole substituted zinc phthalocyanine (2, containing two charges, and 3, containing four charges) are reported in this work. Furthermore, the activity of the synthesized complex was compared to non-quaternary derivative (1). Higher triplet and singlet oxygen quantum yields of 0.92 and 0.85, respectively, for quaternized complexes 2 and 3 compared to complex 1 alone. Complexes 1, 2 and 3 showed relatively no dark toxicity against the epithelial breast cancer cells with cell survival of above 90 ± 3%. The quaternary derivatives (2 and 3) showed superior PDT activity with 30% or less of viable cells at concentration of 50.0 μg/mL in comparison to complex 1 alone which further lay credence to the importance of quaternization in the enhancement of PDT activity.

We report on the electrochemical behaviour of reduced graphene quantum dots (rGQDs) compared to amino functionalized graphene quantum dots (NH2GQDs). Reduction of the GQDs entails the elimination of the excessive carboxyl and hydrogen groups on the GQDs surface, thereby reducing the energy band gap. The energy band gap of graphene is directly proportional to the available oxygen atoms. The two GQD types were conjugated to a novel cobalt phthalocyanine (cobalt tris-(tert-butyl phenoxy)-mono-carboxyphenoxy phthalocyanine, CoPc) via covalent and nom-covalent interactions. The resulting conjugates were tested towards the electrooxidation of hydrazine. The conjugates are represented as rGQDs(π)CoPc, NH2(π)CoPc, rGQDs@CoPc and NH2GQDs@CoPc. The resulting conjugates were adsorbed onto a glassy carbon electrode using the drop and dry method. The lowest limit of detection (LOD) was obtained for rGQDs(π)CoPc.

Unsubstituted zinc phthalocyanine (ZnPc), 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) and Zn tetrasulfo phthalocyanine (ZnTSPc) were non-covalently (electrostatic and/or π–π interaction) attached to graphene quantum dots (GQDs) to form GQDs-Pc nanoconjugates. Relative to Pcs alone, the presence of GQDs improved the triplet quantum yields with the following values: GQDs-ZnPc (0.73), GQDs-ZnTPPcQ (0.76) and GQDs-ZnTSPc (0.67). Respective Förster resonance energy transfer (FRET) efficiencies were calculated to be 0.81, 0.80 and 0.28. However, singlet oxygen generating abilities of the as-synthesized nanoconjugates were relatively low due to the screening effect of GQDs and quenching in water. This study shows that, the type of Pc, loading and solvent used are among the vital properties to consider when constructing GQD-nanoconjugate systems with optimal triplet quantum yield properties and investigation of their physicochemical properties.

This work reports on the synthesis of nanoassemblies of supramolecular hybrids containing detonated nanodiamonds (DNDs) covalently linked to halogenated BODIPY (DNDs-BODIPY) by an amide bond, followed by π–π stacking of 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) on the DNDs-BODIPY conjugate, to form nanoassembly represented as ZnTPPcQ-DNDs-BODIPY. ZnTPPcQ-DNDs-BODIPY has a higher singlet oxygen quantum yield of 0.50 in water. Therefore, the construction of a three component photodynamic therapy agent (ZnTPPcQ-DNDs-BODIPY) as a single photosentisiser improved singlet quantum yields of the Pc. Zeta potential studies of ZnTPPcQ-DNDs-BODIPY under various temperatures, concentrations and pH conditions, showed the conjugate is more stable at pHs 2, 4 and 7 and at high concentrations (50 μg/mL) and temperatures (80 °C). ZnTPPcQ-DNDs-BODIPY showed high photodynamic therapy (PDT) activity with a low MCF-7 cell viability of 21 ± 5% when compared to 31 ± 2%, 30 ± 2% and 28 ± 2% cell viability at the highest tested concentration of 50 μg/mL for DNDs, ZnTPPcQ-DND and DNDs-BODIPY, respectively.

An amide mono substituted benzothiozole phthalocyanine: zinc(II) 3-(4-((3,17,23-tris(4-(benzo [d]thiazol-2-yl)phenoxy)-9-yl)oxy) phenyl)amide phthalocyanine (NH2BzPc) was covalently linked to undoped and heteroatom doped detonation nanodiamonds (DNDs): B@DNDs, P@DNDs, S@DNDs, N@DNDs, and S&N@DNDs There is a drastic decrease in highest occupied molecular orbital (HOMO) – lowest unoccupied molecular orbital (LUMO) energy gaps for nanoconjugates compared to DNDs alone. B@DNDs-NH2BzPc, S&N@DNDs-NH2BzPc, and P@DNDs-NH2BzPc showed superior photodynamic therapy (PDT) effects. DNDs-NH2BzPc also had a small HOMO-LUMO gap, but did not show improved PDT activity compared to the Pc alone, suggesting doping of DNDs is important. This study shows improved PDT effect on Michigan Cancer Foundation-7 breast cancer lines at 7.63%, 7.62% and 6.5% cell viability for P@DNDs-NH2BzPc, S&N@DNDs-NH2BzPc and B@DNDs-NH2BzPc, respectively.

This work reports on the photophysical, nonlinear absorption and optical limiting properties of detonation nanodiamonds (DNDs)-silicon phthalocyanine nanoconjugate systems. Si(IV) hydroxide phthalocyanines employed are: 2,9(10),16(17),23(24)-tetrakis-(4-pyridyloxy) phthalocyaninato (Si(OH)2TPPc), 2,9(10),16(17),23(24)-tetrakis-(4-tert-butyl) phthalocyanato (Si(OH)2TBPc) and phthalocyanato(Si(OH)2Pc). Pcs were covalently linked to nanondiamonds and investigated using 532 nm laser excitation at 7 ns pulses for their optical limiting properties. Si(OH)2TBPc and Si(OH)2Pc gave larger triplet quantum yields when linked to DNDs, while the value decreased for Si(OH)2TPPc in the presence of DNDs due to aggregation. However all Pcs showed enhanced nonlinear optical properties in the presence of DNDs. DNDs-Si(OH)2TPPc and DNDs-Si(OH)2TBPc gave the highest imaginary third-order susceptibility (Im[X(3)]) and hyperpolarizability ( γ ) at 5.19 × 10−8 and 3.85 × 10−8 esu and 2.66 × 10−27 and 1.97 × 10−27 esu, respectively. DNDs-Si(OH)2TBPc nanoconjugates showed lowest limiting threshold (Ilim) value of 0.01 J.cm−2 relative to 0.09 for DNDs-Si(OH)2TPPc.

A positively charged phthalocyanine (2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ)) was non-covalently linked to carbon based nanoparticles: detonation nanodiamonds (DNDs), carbon dots (CDs) and graphene quantum dots (GQDs) to form nanosembles of DNDs-ZnTPPcQ, GQDs-ZnTPPcQ and CDs-ZnTPPcQ, respectively. Irrespective of its small size and the least number of Pcs (41.67 μg loading per milligram of DNDs), DNDs-ZnTPPcQ gave the highest singlet oxygen quantum yield (0.62) in dimethyl sulfoxide compared to the rest of the conjugates. This resulted in superior PDT activity against MCF7 breast cancer lines, with the lowest cell viability of 28% compared to ZnTPPcQ-CDs and ZnTPPcQ-GQDs at 30.1 ± 0.02% and 31.4 ± 0.23%, respectively.

Various sizes of graphene quantum dots (GQDs) denoted as GQD2, GQD6 and GQD10 (increasing in size) were non-covalently attached to 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) to form GQDs-ZnTPPcQ nanoconjugates. X-ray photoelectron spectroscopy (XPS) showed that increasing sizes of GQDs decreases the atomic concentrations of oxygen, which leads to blue shift in spectra of the GQDs. Relative to Pcs alone (0.03), the presence of GQDs improved the singlet oxygen quantum yields with the following values: GQD2-ZnTPPcQ (0.17), GQD6-ZnTPPcQ (0.27) and GQD10-ZnTPPcQ (0.11). GQD2-ZnTPPcQ nanoconjugate system had the most ZnTPPcQ loading, but did not generate the most singlet oxygen species due to aggregation. This study shows that, the quantity of oxygen, size and quality of GQDs as well as amount of Pc loading are amongst the vital properties to consider when constructing GQD-nanoconjugate systems with optimal singlet oxygen quantum yields.