Synthesis of amphiphilic meso-tetrasubstituted porphyrin-L-amino acid and -heterocyclic conjugates based on m-THPP

Two series of amphiphilic meso-tetrasubstituted porphyrin conjugates based on 5,10,15,20-tetrakis(3-hydroxyphenyl)porphyrin ([Formula: see text]-THPP) covalently linked to L-amino acids and heterocycles were synthesized efficiently in the context of a program targeting new photosensitizers for PDT. 5,10,15-Tris(3-hydroxyphenyl)-20-(3-oxyacetic acid)phenyl]porphyrin and the respective trihexyl ether derivatives were conjugated with polar and non-polar natural L-amino acids such as glycine, L-proline, and L-tyrosine via an amide bond linker using [Formula: see text]-tetramethyl-[Formula: see text]-(1H-benzotriazol-1-yl)uroniumhexafluorophosphate in diisopropylethylamine (HBTU/DIPEA). [Formula: see text]-THPP was also conjugated with heterocyclic systems such as indole 3-acetic acid, 4-methylthiazole-5-carboxylic acid, and thiophene-2-carboxylic acid via ester linker using [Formula: see text]-(3-dimethylaminopropyl)-[Formula: see text]-ethylcarbodiimide hydrochloride in [Formula: see text]-hydroxysuccinamide or 1-hydroxybenzotriazole (EDCI, NHS or HOBt). The members of the two series were obtained in good yields and characterized by UV-vis, HRMS MALDI-TOF, 1H NMR and 13C NMR spectroscopy.

Hydrogen sulfide in the mouse ductus arteriosus: a naturally occurring relaxant with potential EDHF function

We have previously reported that bradykinin relaxes the fetal ductus arteriosus via endothelium-derived hyperpolarizing factor (EDHF) when other naturally occurring relaxants (prostaglandin E2, nitric oxide, and carbon monoxide) are suppressed, but the identity of the agent could not be ascertained. Here, we have examined in the mouse whether hydrogen sulfide (H2S) is a relaxant of the ductus and, if so, whether it may also function as an EDHF. We found in the vessel transcripts for the H2S synthetic enzymes, cystathionine-γ-lyase (CSE) and cystathionine-β-synthase (CBS), and the presence of these enzymes was confirmed by immunofluorescence microscopy. CSE and CBS were distributed across the vessel wall with the former prevailing in the intimal layer. Both enzymes occurred within the endoplasmic reticulum of endothelial and muscle cells, whereas only CSE was located also in the plasma membrane. The isolated ductus contracted to inhibitors of CSE (d,l-propargylglycine, PPG) and CBS (amino-oxyacetic acid), and PPG contraction was attenuated by removal of the endothelium. EDHF-mediated bradykinin relaxation was curtailed by both PPG and amino-oxyacetic acid, whereas the relaxation to sodium nitroprusside was not affected by either treatment. The H2S donor sodium hydrogen sulfide (NaHS) was also a potent, concentration-dependent relaxant. We conclude that the ductus is endowed with a H2S system exerting a tonic relaxation. In addition, H2S, possibly via an overriding CSE source, qualifies as an EDHF. These findings introduce a novel vasoregulatory mechanism into the ductus, with implications for antenatal patency of the vessel and its transitional adjustments at birth.

Effects of Anti-Ethylene Treatments on Ethylene Production and Antioxidant Activities in Cut Spray Carnation

The present investigation was aimed to study changes in ethylene production, ACC content and antioxidant enzymes of cut spray carnation (Dianthus caryophyllus L.) flowers that had been treated with amino-oxyacetic acid (AOA), benzyladenine (BA) and 1-methylcyclopropene (1-MCP). Maximum vase life in ‘Optima’ spray carnations was obtained with 0.6 mg l-1 1-MCP. Ethylene production was significantly decreased by AOA at concentrations over 100 mg l-1, BA at 30 mg l-1, and 1-MCP at all concentrations, compared with the control. A significant increase in ACC content was observed in 1-MCP treated cut flowers compared with the control. However, the decline in ACC content was observed after using 100 or 150 mg l-1 AOA. A significant increase in SOD, CAT and POX enzyme activities was observed in the treatment with 0.6 mg l-1 1-MCP.