Synthesis of New Cobalt(III) Meso-Porphyrin Complex, Photochemical, X-ray Diffraction, and Electrical Properties for Photovoltaic Cells.

The present work describes the preparation and characterization of a new cobalt(III) porphyrin coordination compound named (chlorido)(nicotinoylchloride)[meso-tetra(para-chlorophenyl)porphyrinato]cobalt(III) dichloromethane monosolvate with the formula [CoIII(TClPP)Cl(NTC)]·CH2Cl2 (4). The single-crystal X-ray molecular structure of 4 shows very important ruffling and waving distortions of the porphyrin macrocycle. The Soret and Q absorption bands of 4 are very red-shifted as a consequence of the very distorted porphyrin core. This coordination compound was also studied by fluorescence and cyclic voltammetry. The efficiency of our four porphyrinic compounds-the H2TClPP (1) free-base porphyrin, the [CoII(TClPP)] (2) and [CoIII(TClPP)Cl] (3) starting materials, and the new Co(III) metalloporphyrin [CoIII(TClPP)Cl(NTC)]·CH2Cl2 (4)-as catalysts in the photochemical degradation was tested on malachite green (MG) dye. The current voltage of complexes 3 and 4 was also studied. Electrical parameters, including the saturation current density (Js) and barrier height (ϕb), were measured.

Synthesis and SPAR exploration of new semicarbazone-triazole hybrids in search of potent antioxidant, antibacterial and antifungal agents.

A new series of semicarbazone-triazole hybrid derivatives have been synthesized by condensation between heterocyclic aldehydes and the commercial semicarbazide hydrochloride. The in vitro antioxidant activity of these species was tested using 1,1-diphenyl-2-picrylhydrazyl radical, 2,2'-Azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) and Ferric reducing antioxidant power assays and their antimicrobial activity against different microbial strains was carried out. Furthermore, molecular properties prediction and drug likeness were also determinated using Molinspiration. Among such derivatives, compounds (E)-2-(4-((1-(2,6-dimethylphenyl)-1H-1,2,3-triazol-4-yl)methoxy)benzylidene)hydrazine carboxamide (4c), and (E)-2-(4-((1-(2-methoxyphenyl)-1-H-1,2,3-triazol-4-yl)methoxy)benzylidene)hydrazine-carboxamide (4e) exhibit excellent scavenging ability, especially with IC50 = 1.57 ± 1.66 mg/mL (4c) and IC50 = 1.82 ± 0.15 mg/mL (4e) with 1,1-diphenyl-2-picrylhydrazyl radical and IC50 = 1.90 ± 1.33 mg/mL (4c) with 2,2'-Azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) as compared to the standards butylhydroxytoluene (IC50 = 1.60 ± 1.98 mg/mL) and Trolox (IC50 = 1.45 ± 1.33 mg/mL), respectively. The antimicrobial assay results, show that compounds 4c and 4e highlighted the most interesting profile with the potent activity was obtained against S. enteritidis (1.56-fold) and then M. luteus (1.45-fold) which are significantly higher than the positive control, chloramphenicol. By the other hand, the synthesized semicarbazone derivatives met the Lipinski's rule criteria by presenting good drug likeness and bioactivity scores. The structure-property-activity relationships have been carried out in order to determine the effect of various substituents on the molecular and the biological properties. All these investigations confirm that our synthetic semicarbazone can be explored for generating new potential drug with good oral bioavailability.

Diaqua-(5,10,15,20-tetra-phenyl-porphyrinato-κ(4)N)magnesium-18-crown-6 (1/1).

In the title compound, [Mg(C(44)H(28)N(4))(H(2)O)(2)]·C(12)H(24)O(6), the Mg(II) cation lies on an inversion center and is octa-hedrally coordinated by the four N atoms of the deprotonated tetra-phenyl-porphyrin (TPP) ligand and by two water mol-ecules. The asymmetric unit contains one half of the [Mg(TPP)(H(2)O)(2)] complex and one half of an 18-crown-6 mol-ecule. The average equatorial magnesium-pyrrole N atom distance (Mg-N(p)) is 2.071 (1) Šand the axial Mg-O(H(2)O) bond length is 2.213 (1) Å. The crystal packing is stabilized by two O-H⋯O hydrogen bonds between coordinating water mol-ecules and adjacent 18-crown-6 mol-ecules, and exhibits a one-dimensional supramolecular structure along the a axis. The supramolecular architecture is futher stabilized by weak C-H⋯π inter-actions. The 18-crown-6 mol-ecule is disordered over two sets of sites with an occupancy ratio of 0.8:0.2.

Synthesis and crystal structure of bis-(tert-butyl isocyanide-κC)[5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinato-κ4N]iron(II).

In the title compound, [FeII(C44H24Cl4N4)(C5H9N)2] or [FeII(TClPP)(t-BuNC)2] [where TClPP and t-BuNC are 5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinate and tert-butyl isocyanide ligands, respectively], the metal ion lies on an inversion center and is octa-hedrally coordinated by the N atoms of the porphyrin ring in the equatorial plane and by carbon atoms of the trans t-BuNC ligands in the axial sites. The Fe-N bond length of 2.0074 (14) Šsuggests a low-spin complex (S = 0). The crystal packing of the title compound is sustained by C-H⋯Cl, C-H⋯N and C__H⋯Cg (Cg = the centroid of a pyrrole ring of the TClPP porphyrinate) inter-actions, leading to a three-dimensional network. The Hirshfeld surface (HS) analysis indicates that 61.4% of the inter-molecular inter-actions are from H⋯H contacts while other contributions are from C⋯H/H⋯C, O⋯H/H⋯O and N⋯H/H⋯N inter-actions, which comprise 21.3%, 13.3% and 3.6% of the HS, respectively.

[Wernicke's encephalopathy: a rare complication of hyperemesis gravidarum]. / Encéphalopathie de Wernicke: complication rare de l'hyperemesis gravidarum.

Wernicke's encephalopathy is a deficiency disease resulting from severe thiamine deficiency (vitamin B1). It mainly occurs in alcoholic subjects, but sometimes it is difficult to diagnose. The absence of treatment leads to severe cognitive sequelae. Magnetic resonance imaging is the gold standard imaging modality to confirm the diagnosis. The diagnostic sign is T2-weighted hyperintensity in the periaqueducal, thalami and mammillary bodies. We report the case of a 30-year-old woman with abundant vomiting during the first trimester of pregnancy (hyperemesis gravidarum), causing symptomatic Wernicke's encephalopathy.

Effect of the coordination of π-acceptor 4-cyanopyridine ligand on the structural and electronic properties of meso-tetra(para-methoxy) and meso-tetra(para-chlorophenyl) porphyrin cobalt(ii) coordination compounds. Application in the catalytic degradation of methylene blue dye.

To examine the influence of both the important π-acceptor character of the 4-cyanopyridine ligand and the nature of the para-substituted phenyls of meso-porphyrins on the electronic, electrochemical and structural properties of cobaltous metalloporphyrins, we prepared and fully characterized two coordination compounds: the (4-cyanopyridine)[meso-tetra(para-methoxyphenyl)porphyrinato]cobalt(ii) and the (4-cyanopyridine)[meso-tetra(para-chlorophenyl)porphyrinato]cobalt(ii) with the [CoII(TMPP)(4-CNpy)] and [CoII(TClPP)(4-CNpy)] formulas (complexes 1-2). The solution structures of compounds 1-2 were confirmed by 1H NMR spectroscopy and mass spectrometry methods. They were further characterized by cyclic voltammetry and photoluminescence studies. The X-ray molecular structure data show that the Co-TClPP-4-NCpy derivative (2) exhibits high ruffling deformation compared to that of the Co-TMPP-4-CNpy species (1). Notably, the crystal packing of complex 1 shows the formation of Co⋯Co supramolecular dimers with a distance of 5.663 Å. As an application of our two cobaltous compounds, an investigation involving complexes 1-2 in the degradation of the methylene blue dye in the presence and absence of H2O2 in aqueous solutions was carried out. These promising results show that 1-2 can be used as catalysts in the degradation processes of dyes.

Zinc(ii) triazole meso-arylsubstituted porphyrins for UV-visible chloride and bromide detection. Adsorption and catalytic degradation of malachite green dye.

Three new triazole meso-arylporphyrins (4a-c) were synthesized by the copper(i)-catalyzed azide alkyne cycloaddition (CuAAC) "click" reaction in high yield. The corresponding zinc(ii) coordination compounds (5a-c) have also been prepared. All 4a-c and 5a-c porphyrin species were fully characterized by elemental analysis, electrospray ionization and MALDI-TOF mass spectrometry, infrared spectroscopy, proton nuclear magnetic resonance, UV-visible, fluorescence and cyclic voltammetry. The zinc(ii) 5a-c complexes have been tested as detectors for Cl- and Br- anions. UV-visible titrations reveal that these host systems exhibit strong anion binding affinities. The efficiency of the adsorption of the malachite green dye (MG) dye on the 4a-c free base porphyrins and the corresponding zinc(ii) complexes 5a-c was investigated by a kinetic study using these synthetic porphyrin derivatives as adsorbents. The use of our triazole Zn(ii) complexes in the catalytic degradation of the MG dye is the first example where a metalloporphyrin is involved in the MG dye decolorization reaction. The degradation reactions were carried out using an ecological oxidant (H2O2), where the efficiency of the decolorization has been characterized by UV-visible spectroscopic analysis. Several factors affecting the degradation phenomenon have been studied. The energetic parameters concerning the degradation process have also been determined.

Rare synovium pseudotumor of the knee.

It is a rare synovium pseudotumor that mainly concerns the male adult, of unknown etiology, espe-cially observed in the knee, especially in the suprapatellar recess. The arboreal lipoma consists of hypertrophic synovial villi and contains fat in very large quantities, so that the mass has a lipoma-tous appearance. The diagnosis is based on an MRI that shows hypertrophy of synovial villi appear-ing as a fatty signal on all sequences. However the diagnosis is established after synovial biopsy.

Extra bone chondroma of the shoulder: a case study and literature review.

Extra-osseous chondroma is a benign and rare tumor. It usually sits at the extremities, we report an exceptional case of a chondroma of the soft parts of the shoulder in a 28 year old woman who manifested by a painless swelling of the left shoulder. The histology confirmed the diagnosis on the excision piece. Clinical and radiological follow-up after a 24-month follow-up did not show a sign of recurrence.

In vitro anticancer activity of new gold(III) porphyrin complexes in colon cancer cells.

Colorectal cancer (CRC) is the third most common cancer diagnosed worldwide. The limitations of cisplatin-based chemotherapy have prompted intense interest among scientists to search for alternative metal-based anticancer medicines. Gold(III) complexes have been among the most widely investigated since they showed higher cytotoxicity than cisplatin and promising in vitro and in vivo anticancer activities in CRC but their clinical usefulness has been limited by their poor stability under physiological conditions. A novel gold(III) porphyrin complexes [gold(III) porphyrin-adamantane chloride (SN1) and gold(III) porphyrin mono-acetate chloride (SN2)] with improved aqueous stability were synthesized. SN1 and SN2 reduced the survival of human CRC HT-29 and HCT-116 cell lines, caused cell cycle arrest in G2/M phase, and we observed downregulation of the expression of cyclin B1 and cyclin-dependent kinase 1 (Cdk1) along with up-regulation of the active form of p53, p21 and Bcl-2-associated X (Bax). Furthermore, SN1 and SN2 induced apoptosis by the intrinsic pathway, since they lead to the cleavage of caspase 9, caspase 3 and poly(ADP-ribose) polymerase (PARP), and up-regulating Bax. Phosphatidylinositol-3-kinase/protein kinase B (PI3K/Akt), nuclear factor-κB (NF-κB) and extracellular signal-regulated kinases (ERK) are important for cell survival and proliferation. SN1 and SN2 lead to decrease in the activity of Akt where the phosphorylated form decreased with time as well as they caused an important decrease in the phosphorylation of ERK and activity of NF-κB. Finally, SN1 and SN2 complexes affected p38/mitogen-activated protein kinase (MAPK) pathway then we recorded an increase in the cyclooxygenase-2 expression and its enzymatic product prostaglandin E2.

Crystal structure of (4-cyano-pyridine-κN){5,10,15,20-tetrakis[4-(benzoyloxy)phenyl]porphyrinato-κ(4) N}zinc-4-cyano-pyridine (1/1).

In the title compound, [Zn(C72H44N4O8)(C6H4N2)]·C6H4N2 or [Zn(TPBP)(4-CNpy]·(4-CNpy) [where TPBP and 4-CNpy are 5,10,15,20-(tetra-phenyl-benzoate)porphyrinate and 4-cyano-pyridine, respectively], the Zn(II) cation is chelated by four pyrrole-N atoms of the porphyrinate anion and coordinated by a pyridyl-N atom of the 4-CNpy axial ligand in a distorted square-pyramidal geometry. The average Zn-N(pyrrole) bond length is 2.060 (6) Šand the Zn-N(4-CNpy) bond length is 2.159 (2) Å. The zinc cation is displaced by 0.319 (1) Šfrom the N4C20 mean plane of the porphyrinate anion toward the 4-cyano-pyridine axial ligand. This porphyrinate macrocycle exhibits major saddle and moderate ruffling and doming deformations. In the crystal, the [Zn(TPBP)(4-CNpy)] complex mol-ecules are linked together via weak C-H⋯N, C-H⋯O and C-H⋯π inter-actions, forming supra-molecular channels parallel to the c axis. The non-coordinating 4-cyano-pyridine mol-ecules are located in the channels and linked with the complex mol-ecules, via weak C-H⋯N inter-actions and π-π stacking or via weak C-H⋯O and C-H⋯π inter-actions. The non-coordinating 4-cyano-pyridine mol-ecule is disordered over two positions with an occupancy ratio of 0.666 (4):0.334 (4).

Crystal structure of an unknown solvate of (piperazine-κN){5,10,15,20-tetra-kis-[4-(benzo-yloxy)phen-yl]porphyrinato-κ(4) N}zinc.

The title compound, [Zn(C72H44N4O8)(C4H10N2)] or [Zn(TPBP)(pipz] (where TPBP and pipz are 5,10,15,20-tetra-kis-[4-(benzo-yloxy)phen-yl]porphyrinato and piperazine ligands respectively), features a distorted square-pyramidal coordin-ation geometry about the central Zn(II) atom. This central atom is chelated by the four N atoms of the porphyrinate anion and further coordinated by a nitro-gen atom of the piperazine axial ligand, which adopts a chair confirmation. The average Zn-N(pyrrole) bond length is 2.078 (7) Šand the Zn- N(pipz) bond length is 2.1274 (19) Å. The zinc cation is displaced by 0.4365 (4) Šfrom the N4C20 mean plane of the porphyrinate anion toward the piperazine axial ligand. This porphyrinate macrocycle exhibits major saddle and moderate ruffling deformations. In the crystal, the supra-molecular structure is made by parallel pairs of layers along (100), with an inter-layer distance of 4.100 Šwhile the distance between two pairs of layers is 4.047 Å. A region of electron density was treated with the SQUEEZE [Spek (2015 ▸). Acta Cryst. C71, 9-18] procedure in PLATON following unsuccessful attempts to model it as being part of disordered n-hexane solvent and water mol-ecules. The given chemical formula and other crystal data do not take into account these solvent mol-ecules.

Crystal structure of (1S,2S,2'R,3a'S,5R)-2'-[(5-bromo-1H-indol-3-yl)meth-yl]-2-isopropyl-5,5'-dimethyl-dihydro-2'H-spiro-[cyclo-hexane-1,6'-imidazo[1,5-b]isoxazol]-4'(5'H)-one.

In the title compound, C24H32BrN3O2, the six-membered cyclo-hexane ring adopts a chair conformation and the isoxasolidine ring adopts a twisted conformation. The mol-ecule has five chiral centres and the absolute configuration has been determined in this analysis. The mol-ecular structure is stabilized by weak intra-molecular C-H⋯O and C-H⋯N contacts. In the crystal, mol-ecules are linked by N-H⋯N and C-H⋯O hydrogen bonds, forming undulating sheets parallel to the bc plane.

Crystal structure of 5-chloro-methyl-N-methyl-4-[(4-phenyl-1,2,3-triazol-1-yl)meth-yl]isoxazolidine-3-carboxamide.

The title compound, C15H18ClN5O2, crystallizes with two independent mol-ecules (A and B) in the asymmetric unit. In both mol-ecules, the isoxazolidine rings have an envelope conformation with the O atoms at the flap positions. Each mol-ecule has three stereogenic centres with configurations 2(S), 3(S) and 4(R), confirmed by resonant scattering. Their conformations are significantly different, for example in mol-ecule A the phenyl ring is inclined to the triazole ring by 32.5 (2)°, while in mol-ecule B the corresponding dihedral angle is 10.7 (2)°. In the crystal, the A and B mol-ecules are linked via an N-H⋯O and a C-H⋯O hydrogen bond. These units are linked by C-H⋯O and C-H⋯N hydrogen bonds, forming slabs parallel to the ab plane. There are C-H⋯π inter-actions present within the slabs.