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In the present study, we describe the synthesis and characterization of a new covalent organic framework (COF-TPP-CB[6]) which was assembled together by clicking perpropargyloxy cucurbit[6]uril (CB[6]) to the azido-functionalized tetraphenylporphyrin (TPP-4N3) through a copper-catalyzed azide–alkyne cycloaddition reaction (CuAAC). Perpropargyloxy CB[6] was synthesized through the direct oxidation of CB[6] to afford perhydroxy CB[6] followed by subsequent O-propargylation using NaH. We also demonstrated that the resulting framework (COF-TPP-CB[6]) can be employed as an efficient and stable electrocatalyst for hydrogen evolution reaction (HER) in alkaline medium upon loading it with a nickel cocatalyst. The effect of TiO2 and different loadings of Ni on the HER performance of TPP-CB[6] was also studied. Herein, 12%Ni@TPP-CB[6] as the optimum catalyst showed an impressive H2 production rate of 18.7 mmol h–1 g–1 with a low onset potential of −250 mV.

Here, we adapt the catalytically self-threading polyrotaxane synthesis for the construction of two-dimensional polymeric thin films using a water−oil interfacial polymerization method. In this method, the polymerization and the rotaxane formation take place simultaneously at the interface because of the presence of catalytically active cucurbit[6]uril (CB6) that can facilitate 1,3-dipolar cycloaddition reaction between alkyne and azide to form polytriazoles. By varying the concentration of the monomers, reaction time, and the size of the reaction vessel, it is possible to control the thickness and the lateral dimensions of the film. The as-synthesized film is free-floating, transparent, and robust enough to be transferred to any substrates. It contains photoactive porphyrin units which are quite appealing as a photosensitizer because of their capability to produce reactive oxygen species in high yield upon visible light irradiation. By taking advantage of these aforementioned features, this film was employed as a broad-spectrum photo-antimicrobial agent whose activity was switched on by light excitation against both Gram-negative and Gram-positive bacterial strains and switched off in the dark.

We report here the synthesis and characterization of a water dispersible conjugated polymer nanoparticle-based photosensitizer and its application in the antibacterial and anticancer phototherapies. Nanoparticles (CPPN) were synthesized in one-pot by nanoprecipitation method, in which a hydrophobic azide functionalized, red-emitting thiophene-benzothiodiazole based conjugated polymer (CP-AZ) was cross-linked with a hydrophilic, propargylamine functionalized porphyrin (TPP-4AL) through cucurbit[6]uril (CB6) catalyzed azide-alkyne cycloaddition (CB6-AAC) reaction. CPPN demonstrated high stability in aqueous medium for more than a month without any visible aggregation and appeared to be a good photosensitizer with high light-triggered reactive oxygen species (ROS) generation ability. Consequently, CPPN displayed photo-induced biocidal activity against Gram-negative (Escherichia coli, E. coli) and Gram-positive (Bacillus subtilis, B. subtilis and Staphylococcus aureus, S. aureus) bacteria. When bacteria suspension was incubated with CPPN (20 μg ml−1) and irradiated with white light (22 mW cm−2) for 10 min, more than 3.5-log reduction in colony-forming units (CFUs) was recorded for the three model bacteria. CPPN demonstrated minimal dark cytotoxicity against the bacteria. Moreover, the cytotoxicity of CPPN on mammalian cell was studied using MCF-7 breast cancer cell line. The results demonstrated that CPPN is non-toxic to mammalian cells in the dark even at a high concentration of 112.5 μg ml−1 and this feature makes CPPN an ideal photosensitizer.

Here we report the preparation of water-dispersible glycosylated poly(2,5'-thienylene) porphyrin based nanoparticles by a nanoprecipitation method and demonstrate the application of these nanoparticles in antibacterial photodynamic therapy. The diameter of the nanoparticles is in the range of 50-80 nm and the resulting nanoparticles are stable in water without precipitation at least for a month. They have high singlet oxygen efficiency and display light-triggered biocidal activity against both Gram negative bacteria (Escherichia coli, E. coli) and Gram positive bacteria (Bacillus subtilis, B. subtilis). Upon white light irradiation for 10 min with a flux of 22 mW cm(-2) of the E. coli suspension incubated with NPs (18 mu g mL(-1)), a killing efficiency of 99% is achieved, whereas in the dark the effect is recorded as only around 8%.

Herein, we report the synthesis of a new supramolecular polymeric network (PCN) assembled through cross linking of propyl bromide substituted tetraphenyl porphyrin with perhydroxy-cucurbit [8]uril and its use in the electrocatalytic hydrogen evaluation reaction after loading with nickel and integrating with in situ -electrochemically reduced graphene oxide (ERGO). Electrode was prepared by first coating graphene oxide on the FTO substrate followed by layering the nickel loaded PCN and finally by applying an appropriate voltage to reduce the graphene oxide in situ electrochemical reaction. The loading of nickel cocatalyst into PCN together with the integration of ERGO layer substantially improved its HER efficiency. Effect of various concentrations of Ni and GO on the HER activity of the developed electrocatalyst were investigated. Therein, ERGO(1)/Ni-2@PCN catalyst containing 41% Ni and 50% GO (with respect to PCN) with only one layer of each component demonstrated excellent HER activity and stability with low onset and overpotentials of -20 mV, eta@10 mA cm(-2) of -360 mV, respectively, and remarkable hydrogen generation rate of 27.5 mmol h(-1) g(-1) in 1 M KOH. This noble-metal-free catalytic system is simple yet highly promising for the efficient hydrogen evolution reaction from water splitting.

Visible‐light triggerable, stable, organic material‐based photocatalysts that can function in alkaline media without the necessity of sacrificial agent for hydrogen production are highly sought after. Here, we report a novel supramolecular photocatalyst that confers the aforementioned features. This supramolecular photocatalyst (TPP‐4CB7) is synthesized through the conjugation of monohydroxylated cucurbit(7)uril (CB7) hosts to a suitably substituted tetraphenyl porphyrin. Although TPP‐4CB7 by its own preforms as an efficient visible light triggered photocatalyst, the hydrogen production efficiency is significantly enhanced upon mixing with TiO2. The resulting nanocomposite (TPP‐CB‐TiO2@Pt) is observed to exhibit remarkable electrophotocatalytic activity under visible light and produces hydrogen (onset potential −10 mV, turn over frequency (TOF) 0.202 s−1, 24.5 mmol h−1 g−1) from water splitting without any significant degradation during four runs (5 h each) in alkaline media and in the absence of sacrificial agent. The Scientific and Technological Research Council of Turkey-TÜBİTAK. Grant Number: KBAG 215Z035