New AB3-type porphyrins with piperidine and morpholine motifs; synthesis and photo-physicochemical and biological properties.

In this study, new unsymmetrical meso-tetraaryl AB3-type porphyrins 1 and 2 were successfully synthesized by the reaction of p-bromobenzaldehyde and p-hydroxybenzaldehyde with pyrrole in propionic acid. AB3-type porphyrin building blocks with hydroxyl functionality (1 and 2) were further used to generate both covalently linked metal free and Zn(II) porphyrins 3-6 having piperidine and morpholine heterocyclic units. These novel compounds were characterized by using 1H NMR, 13C NMR, FT-IR and MALDI-TOF spectrophotometry. The photophysical and photochemical properties of compounds 1-6 were investigated by employing UV-vis absorption and fluorescence emission spectroscopy in tetrahydrofuran (THF). From the view of biological properties, the antioxidant capacities of porphyrins were determined by using DPPH radical scavenging activity and 2 was determined as the most potent porphyrin analog with a value of 98.42% at 200 mg L-1. All the targeted compounds displayed significant DNA nuclease activity. In addition, the antimicrobial potential of compounds 1-6 was also investigated by a micro-dilution process and 2 was found to be the most effective candidate against the tested microbial strains. The newly synthesized porphyrins also showed 100% microbial cell viability inhibition against E. coli at all examined concentrations. In terms of biofilm inhibition activity, the best results for the maximum photodynamic antimicrobial biofilm inhibition of S. aureus and P. aeruginosa were obtained by compound 2 with the values of 99.75% and 93.39%, respectively.

Chemo-photodynamic Activity of Silicon Phthalocyanines Bearing Cyclooxygenase Inhibitors on Colorectal Cancer Cell Lines.

Colorectal cancer ranks as the third most lethal cancer worldwide, resulting in over 1 million cases and 900 000 deaths per year. According to population-based studies, administration of long-term non-steroidal anti-inflammatory drugs (NSAIDs) was proven to reduce the risk of a subject developing colorectal cancer. In the present study, the anti-cancer activity of two different NSAIDs, sulindac- (Pc-1) or diclofenac-substituted (Pc-2) asymmetric silicon phthalocyanine derivatives, was evaluated in four different colorectal cancer cell lines bearing various carcinogenic mutations. In this context, the IC50 values of each compound after 24 and 48 h were determined on HCT116, SW480, LoVo, and HT29 cell lines, and the effects of the compounds on programmed cell death pathways apoptosis and autophagy, their impact on cell cycle progression, and the effect of NSAID moieties they bear on COX-1 and COX-2 proteins were analyzed. In addition, the photophysical and photochemical properties of a synthesized Pc derivative bearing axial diclofenac and triethylene glycol groups (Pc-2) have been investigated, and the compound has been characterized by using different analytical techniques. Our results indicated that both compounds inhibit COX protein expression levels, activate apoptosis in all cell lines, and lead to cell cycle arrest in the G2/M phase, depending on the COX expression profiles of the cell lines, indicating that NSAIDs can be coupled with Pc's to achieve increased anti-cancer activity, especially on cancer cells known to have high COX activity.

BSA/DNA binding behavior and the photophysicochemical properties of novel water soluble zinc(II)phthalocyanines directly substituted with piperazine groups.

In the current research, two novel zinc(II) phthalocyanines (ZnPcs) (1 and 2) directly connecting with 4-(4-methylpiperazin-1-yl)phenyl groups have been synthesized through the Suzuki-Miyaura coupling reaction. These ZnPcs 1 and 2 were converted to their water-soluble derivatives (1Q and 2Q) by quaternization. The photochemical and photophysical properties were determined in DMSO for the non-ionic zinc(II) phthalocyanines (1 and 2) and in both DMSO and aqueous solutions for the quaternized cationic derivatives (1Q and 2Q) to establish their photosensitizer capabilities in photodynamic therapy (PDT). The spectrofluorometric and spectrophotometric techniques were employed for the determination of interaction between water-soluble ZnPcs (1Q and 2Q) and BSA or ct-DNA. The binding constants of these compounds to BSA were found in the order of 108 M-1. The binding constant of the ct-DNA interaction with 2Q (1.09 × 105 M-1) was found higher than 1Q (6.87 × 104 M-1). The thermodynamic constants were determined for both 1Q and 2Q. The endothermic and spontaneous nature of interaction was observed with ct-DNA. Besides, the thermal denaturation and viscosity studies proved the non-intercalative mode of binding for both compounds to ct-DNA.

Alkali Phosphonate Metal-Organic Frameworks.

A new family of porous metal-organic frameworks (MOFs), namely alkali phosphonate MOFs, is reported. [Na2 Cu(H4 TPPA)]⋅(NH2 (CH3 )2 )2 (GTUB-1) was synthesized using the tetratopic 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H8 -TPPA) linker with planar X-shaped geometrical core. GTUB-1 is composed of rectangular void channels with BET surface area of 697 m2 g-1 . GTUB-1 exhibits exceptional thermal stability. The toxicity analysis of the (H8 -TPPA) linker indicates that it is well tolerated by an intestinal cell line, suggesting its suitability for creating phosphonate MOFs for biological applications.