Phthalocyanine Units Research Articles

2D to 3D Reconstruction of Boron-Linked Covalent-Organic Frameworks.

The transformation of two-dimensional (2D) covalent-organic frameworks (COFs) into three-dimensions (3D) is synthetically challenging, and it is typically addressed through interlayer cross-linking of alkene or alkyne bonds. Here, we report the first example of the chemical reconstruction of a 2D COF to a 3D COF with a complete lattice rearrangement facilitated by base-triggered boron hybridization. This chemical reconstruction involves the conversion of trigonal boronate ester linkages to tetrahedral anionic spiroborate linkages. This transformation reticulates the coplanar, closely stacked square cobalt(II) phthalocyanine (PcCo) units into a 3D perpendicular arrangement. As a result, the pore size of COFs expands from 2.45 nm for the initial 2D square lattice (sql) to 3.02 nm in the 3D noninterpenetrated network (nbo). Mechanistic studies reveal a base-catalyzed boronate ester protodeboronation pathway for the formation of the spiroborate structure.

Phthalocyanine Covalent Organic Frameworks: Dimensionality Effect on Third‐Order Nonlinear Optical Properties

AbstractDimensionality of covalent organic frameworks (COFs), in terms of 2D and 3D, must greatly influence their properties and functionalities due to the different electronic and porous structures, but still less investigated in the 20 years history. Herein, on the basis of the imidization reaction of phthalocyanine‐based tetraanhydride monomers with either 1,4‐phenylenediamine or 1,3,5,7‐tetra(4‐aminophenyl)adamantine, 2D and 3D imide‐bonded COFs with sql and pts topology have been prepared to explore their third‐order nonlinear optical (NLO) properties. In contrast to metal‐free analogues, both 2D and 3D copper‐phthalocyanine COFs have the enhanced NLO behaviors according to the open aperture Z‐scan and optical limiting (OL) results recorded under a nanosecond laser at 532 nm. In particular, 2D COFs with strong π–π staking phthalocyanine units show the NLO property with bigger third‐order nonlinear susceptibility (Imχ(3)) and unique reverse saturation absorption response at 1064 nm than that of 3D species with dispersed conjugated modules. Furthermore, femtosecond transient absorption spectra disclose the longer excited lifetimes of copper COFs than metal free samples, helpful in their NLO property. These findings clearly disclose the materials advantages of 2D phthalocyanine COFs toward the NLO characteristics and provide new candidates for OL application.

Immobilising an acid-cleavable dimeric phthalocyanine on gold nanobipyramids for intracellular pH detection and photodynamic elimination of cancer cells.

An acetal-linked dimeric phthalocyanine has been synthesised and immobilised on the surface of gold nanobipyramids. The resulting nanocomposite serves as a highly sensitive probe for intracellular pH through its acid-responsive fluorescence and surface-enhanced Raman scattering signals. The phthalocyanine units released in the acidic intracellular environment can also effectively eliminate the cancer cells upon light irradiation, rendering this simple fabricated nanosystem a bimodal and bifunctional theranostic agent.

Detection and Elimination of Senescent Cells with a Self-Assembled Senescence-Associated β-Galactosidase-Activatable Nanophotosensitizer.

Senescent cells have become an important therapeutic target for many age-related dysfunctions and diseases. We report herein a novel nanophotosensitizing system that is responsive to the senescence-associated β-galactosidase (β-gal) for selective detection and elimination of these cells. It involves a dimeric zinc(II) phthalocyanine linked to a β-galactose unit via a self-immolative linker. This compound can self-assemble in aqueous media, forming stable nanoscale particles in which the phthalocyanine units are stacked and self-quenched for fluorescence emission and singlet oxygen production. Upon internalization into senescent HeLa cells, these nanoparticles interact with the overproduced senescence-associated β-gal inside the cells to trigger the disassembly process through enzymatic cleavage of the glycosidic bonds, followed by self-immolation to release the photoactive monomeric phthalocyanine units. These senescent cells can then be lit up with fluorescence and eliminated through the photodynamic action upon light irradiation with a half-maximal inhibitory concentration of 0.06 μM.

Modulating the Density of Catalytic Sites in Multiple-Component Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction.

It is generally assumed that the more metal atoms in covalent organic frameworks (COFs) contribute to higher activity toward electrocatalytic carbon dioxide reduction (CO2RR) and hindered us in exploring the correlation between the density of catalytic sites and catalytic performances. Herein, we have constructed quantitative density of catalytic sites in multiple COFs for CO2RR, in which the contents of phthalocyanine (H2Pc) and nickel phthalocyanine (NiPc) units were preciously controlled. With a molar ratio of 1/1 for the H2Pc and NiPc units in COFs, the catalyst achieved the highest selectivity with a carbon monoxide Faradaic efficiency (FECO) of 95.37% and activity with a turnover frequency (TOF) of 4713.53 h-1. In the multiple H2Pc/NiPc-COFs, the electron-donating features of the H2Pc units provide electron transport to the NiPc centers and thus improved the binding ability of CO2 and intermediates on the NiPc units. The theoretical calculation further confirmed that the H2Pc units donated their electrons to the NiPc units in the frameworks, enhanced the electron density of the Ni sites, and improved the binding ability with Lewis acidic CO2 molecules, thereby boosting the CO2RR performance. This study provides us with new insight into the design of highly active catalysts in electrocatalytic systems.

Phthalocyanine covalent frameworks doped in PMMA matrix as high performance nonlinear optical limiter

Phthalocyanine compounds are a class of macrocyclic conjugated structures with 18 π-electrons. And have better photophysical properties. However, the π-π electron interactions lead to aggregation between phthalocyanine molecules, which affects optical limiting properties. In this work, the conjugated organic small molecule antiphenylenediamine (PDA) is grafted onto the phthalocyanine conjugate system through the azo condensation reaction, and the covalent organic framework polymer (PDA-InPc) was obtained. Then it is doped into the polymethyl methylmethacrylate (PMMA) matrix to produce a phthalocyanine solid device with different thickness (PMMA-PDA-InPc). The aggregation-free phthalocyanine covalent organic frameworks avoids intramolecular aggregation of the phthalocyanine units, and dispersing it in PMMA solid devices can also reduce intermolecular π-π stacking. As a result, the fluorescence lifetime of PMMA-PDA-InPc is τ1 = 0.52 ns (A1 = 95.71%) and τ2 = 11.5 ns (A2 = 4.29%), indicating that the phthalocyanine conjugated unit exists mainly as monomers (95.71%), while the proportion as aggregates is very small (4.29%). At the input laser energy of 9 μJ, the nonlinear absorption coefficient of PMMA-PDA-InPc device is (2.2 × 10−9 m/W), which is significantly better than PMMA-InPc device (1.0 × 10−9 m/W), indicating that PMMA-PDA-InPc has improved nonlinear absorption and reverse saturation absorption. This design idea of non-aggregated phthalocyanine covalent organic frameworks and its solid device expands a new idea for the development of useable phthalocyanine optical limiters.

Phthalocyanine‐Based 2D Polymer for Ultrafast Nonlinear Optical Application

AbstractStrong ultrafast nonlinear optical (NLO) responses in near‐infrared (NIR) regions and favorable solution processability are two urgent requirements for practical NLO applications, especially for optical limiting (OL) applications. However, simultaneously optimizing these properties remains significant challenging. In this study, the successful synthesis of a phthalocyanine‐based 2D polymer (Pc‐2DP) is reported; its structure features extended π‐electrons delocalization space constructed by topologically integrating the phthalocyanine units into the 2D framework. The as‐prepared few‐layered Pc‐2DP not only exhibits power‐ and wavelength‐dependent NLO properties toward 35 fs ultrafast pulsed laser, but it also demonstrates excellent ultrafast reverse saturable absorption (RSA) responses in NIR regions. The nonlinear absorption coefficients of Pc‐2DP dispersion reach up to 0.12 and 0.19 cm GW−1 at 800 and 1550 nm, respectively, which are much higher than those of the typical MXene (Ti3C2TX) and molybdenum disulfide with hexagonal structure (2H‐MoS2). The obtained NLO devices exhibit remarkable OL performance at 800 nm and, particularly, in the telecommunication region (1300 to 1550 nm), which is highly desired but seldom reported. The study demonstrates that the as‐prepared Pc‐2DP featuring a highly conjugated aromatic framework is a very promising OL material and that this research provides a new strategy for developing high‐performance 2D organic NLO polymers.

Polymeric Phthalocyanine-Based Nanosensitizers for Enhanced Photodynamic and Sonodynamic Therapies.

Photodynamic therapy and sonodynamic therapy are two highly promising modalities for cancer treatment. The latter holds an additional advantage in deep-tumor therapy owing to the deep penetration of the ultrasonic radiation. The therapeutic efficacy depends highly on the photo/ultrasound-responsive properties of the sensitizers as well as their tumor-localization property and pharmacokinetics. A novel nanosensitizer system based on a polymeric phthalocyanine (pPC-TK) is reported herein in which the phthalocyanine units are connected with cleavable thioketal linkers. Such polymer could self-assemble in water forming nanoparticles with a hydrodynamic diameter of 48nm. The degradable and flexible thioketal linkers could effectively inhibit the π-π stacking of the phthalocyanine units, rendering the resulting nanoparticles an efficient generator of reactive oxygen species upon light or ultrasonic irradiation. The nanosensitizer could be internalized into cancer cells readily, inducing cell death by efficient photodynamic and sonodynamic effects. The potency is significantly higher than that of the monomeric phthalocyanine (PC-4COOH). The nanosensitizer could also effectively inhibit the growth of tumor in liver tumor-bearing mice by these two therapies without causing noticeable side effects. More importantly, it could also retard the growth of a deep-located orthotopic liver tumor in vivo by sonodynamic therapy.

Solar driven CO2 reduction with a molecularly engineered periodic mesoporous organosilica containing cobalt phthalocyanine.

A molecular cobalt phthalocyanine (CoPc) catalyst has been integrated in an ethylene-bridged periodic mesoporous organosilica (PMO) to fabricate a hybrid material, CoPc-PMO, that catalyses CO2 reduction to CO in a photocatalytic system using [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) as a photosensitizer and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as an electron donor. CoPc-PMO displays a Co-based turnover number (TONCO) of >6000 for CO evolution with >70% CO-selectivity after 4 h irradiation with UV-filtered simulated solar light, and a quantum yield of 1.95% at 467 nm towards CO. This system demonstrates a benchmark TONCO for immobilised CoPc-based catalysts towards visible light-driven CO2 reduction.

A Tumor-Targeting Dual-Stimuli-Activatable Photodynamic Molecular Beacon for Precise Photodynamic Therapy.

A multifunctional photodynamic molecular beacon (PMB) has been designed and synthesized which contains an epidermal growth factor receptor (EGFR)-targeting cyclic peptide and a trimeric phthalocyanine skeleton in which the three zinc(II) phthalocyanine units are each substituted with a glutathione (GSH)-responsive 2,4-dinitrobenzenesulfonate (DNBS) quencher and are linked via two cathepsin B-cleavable GFLG peptide chains. This tailor-made conjugate is fully quenched in the native form due to the photoinduced electron transfer effect of the DNBS moieties and the self-quenching of the phthalocyanine units. It can target the EGFR overexpressed in cancer cells, and after receptor-mediated endocytosis, it can be activated selectively by the co-existence of intracellular GSH and cathepsin B, both of which are also overproduced in cancer cells, in terms of fluorescence emission and singlet oxygen generation. The cell-selective behavior of this PMB has been demonstrated using a range of cancer cells with different expression levels of EGFR, while the stimuli-responsive properties have been studied both in vitro and in various aqueous media. The overall results show that this advanced PMB, which exhibits several levels of control of the tumor specificity, is a promising photosensitizer for precise antitumoral photodynamic therapy.

Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage.

Spatial distance is an important factor in controlling the functional interactions between molecular units in a conjugate; therefore, the bridging unit has been closely examined. Here, we examined the effect of the flexibility of bridging alkyl chains on the proximity of stacked porphyrin and phthalocyanine conjugated with a fourfold rotaxane linkage. We found that closely stacking two π systems requires bridging alkyl chains above a certain length, and the shorter bridges hinder stacking because of their lower flexibility. The stacking distance between porphyrin and phthalocyanine in the conjugate with decyl (C10 ) chains was estimated to be 4.03 Å and showed a unique physical character arising from short-distance interactions. The longer alkyl chains minimized steric restriction inside the fourfold rotaxane and allowed efficient communication between the porphyrin and phthalocyanine units. This is due to the flexibility of the side chains.

Hyperbranched phthalocyanine enabling black-phase formamidinium perovskite solar cells processing and operating in humidity open air

The extreme instability of pure α-phase FAPbI3 under high humidity conditions restricts the high-throughput fabrication in unmodified air environments, resulting in poor performance of α-phase FAPbI3 perovskite devices obtained by scalable fabrication methods. Here we synthesized hyperbranched copper phthalocyanine (HCuPc) as a supramolecular additive with twisted phthalocyanine units to realize the molecular-level encapsulation at the grain boundaries through supramolecular interaction, which greatly broadened the processing window of FAPbI3 under high humidity. At the same time, unlike traditional encapsulation layer that carrier can only be collected by tunneling effect, the twisted phthalocyanine ring of HCuPc in perovskite films is more conducive to hole extraction. Finally, a record efficiency was achieved in pure FAPbI3 based inverted structured solar cell by blade-coating to the best of our knowledge, even under unmodified humid air conditions (relative humidity of 65%–85%). The best operational stability of 3D pure FAPbI3 devices can also be achieved at the same time and unencapsulated HCuPc-FAPbI3 device can even operate with negligible degradation for 100 h in the open air (RH 30%–40%).

Dual Cathepsin B and Glutathione-Activated Dimeric and Trimeric Phthalocyanine-Based Photodynamic Molecular Beacons for Targeted Photodynamic Therapy.

Two dual stimuli-activated photosensitizers were developed, in which two or three glutathione (GSH)-responsive 2,4-dinitrobenzenesulfonate (DNBS)-substituted zinc(II) phthalocyanine units were connected via one or two cathepsin B-cleavable Gly-Phe-Leu-Gly peptide linker(s). These dimeric and trimeric phthalocyanines were fully quenched in the native form due to the photoinduced electron transfer to the DNBS substituents and the self-quenching of the phthalocyanine units. In the presence of GSH and cathepsin B, or upon internalization into A549 and HepG2 cancer cells, these probes were activated through the release of free phthalocyanine units. The intracellular fluorescence intensity was increased upon post-incubation with GSH ester or reduced upon pre-treatment with a cathepsin B inhibitor. Upon light irradiation, these photosensitizers became highly cytotoxic with IC50 values of 0.21-0.39 μM. The photocytotoxicity was also dependent on the intracellular GSH and cathepsin B levels. The results showed that these conjugates could serve as smart photosensitizers for targeted photodynamic therapy.

A Cubic 3D Covalent Organic Framework with nbo Topology.

The synthesis of three-dimensional (3D) covalent organic frameworks (COFs) requires high-connectivity polyhedral building blocks or the controlled alignment of building blocks. Here, we use the latter strategy to assemble square-planar cobalt(II) phthalocyanine (PcCo) units into the nbo topology by using tetrahedral spiroborate (SPB) linkages that were chosen to provide the necessary 90° dihedral angles between neighboring PcCo units. This yields a porous 3D COF, SPB-COF-DBA, with a noninterpenetrated nbo topology. SPB-COF-DBA shows high crystallinity and long-range order, with 11 resolved diffraction peaks in the experimental powder X-ray diffraction (PXRD) pattern. This well-ordered crystal lattice can also be imaged by using high-resolution transmission electron microscopy (HR-TEM). SPB-COF-DBA has cubic pores and exhibits permanent porosity with a Brunauer-Emmett-Teller (BET) surface area of 1726 m2 g-1.

Purple silicon(IV) phthalocyanine axially substituted with BODIPY groups

A novel silicon(IV) phthalocyanine axially substituted with iodine containing BODIPY groups was synthesized. Surprisingly, this novel phthalocyanine is colored as purple in solution due to the mixture of pink and blue colours of BODIPY and phthalocyanine units, respectively. Additionally, the photophysical and photochemical properties of this silicon(IV) phthalocyanine were investigated for the determination of its photodynamic therapy (PDT) ability. This phthalocyanine generated approximately 12 times higher singlet oxygen compared to axially non-iodinated BODIPY substituted silicon(IV) phthalocyanine counterpart.

Synthesis, Spectroscopic and Fibroblast Activation Protein (FAP)‐Responsive Properties of Phthalocyanine‐Doxorubicin Conjugates

AbstractA series of novel phthalocyanine‐doxorubicin (Pc‐DOX) conjugates have been prepared with a fibroblast activation protein (FAP)‐sensitive linker of glycine‐proline (Gly‐Pro) dipeptide. Meanwhile, two Pc‐DOX conjugates (1 c and 3 c) without FAP‐sensitive linker have also been prepared for comparison. For Pc‐DOX conjugates, the photosensitizing properties of the phthalocyanines are partly quenched after being conjugated with DOX. The aggregation behavior of these conjugates is less affected by the surfactant of Cremophor EL compared with that of corresponding precursors in aqueous media. The FAP‐responsive properties have been demonstrated by HPLC analysis and fluorescence spectroscopy in phosphate buffered saline. The Pc‐Gly‐Pro‐DOX conjugate 2 b with longer linker is more sensitive to FAP than the other two Pc‐Gly‐Pro‐DOX conjugates (1 b and 3 b). The results suggest that the longer linker and smaller steric hindrance between phthalocyanine and Dox units are beneficial for the cleavage of Gly‐Pro linker induced by FAP, while the axial or peripheral substituted positions hardly allow the enzymolysis of FAP. This work can thus provide a valuable reference for the targeted chemo‐photodynamic therapy of cancer.

Disulfide-Linked Dendritic Oligomeric Phthalocyanines as Glutathione-Responsive Photosensitizers for Photodynamic Therapy.

A series of disulfide-linked dendritic phthalocyanines were synthesized by using the CuI -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 (IC50 ) 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.

Conjugation with L,L-diphenylalanine Self-Assemblies Enhances In Vitro Antitumor Activity of Phthalocyanine Photosensitizer

We present the synthesis and characterization of new peptide conjugates obtained by hierarchical co-assembly of L,L-diphenylalanine (FF) and zinc phthalocyanine complexes (ZnPc) in water. Self-assembly capabilities under defined conditions were investigated by scanning electron microscopy, and photophysical properties were evaluated using UV-Vis and fluorescence spectroscopy. AFM observations demonstrated that these ZnPcs form different highly ordered arrays on the crystalline faces of the FF microplates and that surface roughness significantly changes with the presence of differently substituted phthalocyanine units. XRD assays showed that the overall molecular packing of the conjugates is organized according to a hexagonal symmetry, with ZnPcs hosted in the interstices of the peptide phase. In vitro photodynamic studies were conducted on human breast cancer MCF-7 cells to investigate both cellular uptake and cytotoxicity. It was shown that FF self-assemblies are not toxicity and enhance accumulation of ZnPc in MCF-7 cells, improving apoptotic cell death upon irradiation. Our findings demonstrate enhancement of ZnPc antitumor efficiency by FF conjugates and a proof-of-concept for new photosensitizer carriers based on peptide conjugates.

Catalytic Oxidation of Thiols within Cavities of Phthalocyanine Network Polymers

Two three-dimensional (3D) network polymers (1 and 2), in which zinc(II) or cobalt(II) phthalocyanines were interconnected with twisted 9,9′-spirobifluorene linkers, were synthesized in order to investigate their performance as heterogeneous catalysts for thiol oxidations. From the spectroscopic analyses of two dimers (3 and 4) as component units of the network polymers, 3 connected with a short linker revealed electronic interaction between the two phthalocyanine units. Micrometer-sized polymer particles were formed due to the condensation of the twisted 9,9′-spirobifluorene linkers in the presence of zinc or cobalt ions. The dispersed solutions of 1 and 2 had sharp Q-bands, indicating the prevention of stacking among phthalocyanine moieties within the polymers. Powdered X-ray diffraction pattern and N2 adsorption–desorption analyses suggested that 1 created small and rigid cavities as compared with 2 through the regular spatially arrangement of the phthalocyanine moieties in the 3D networks. The photoca...

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

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.