Synthesis and characterization of tetraphenylporphyrin manganese(III) complexes of phenylcyanamide ligands

Several complexes of TPPMn-L, where TPP is the dianion of tetraphenylporphyrin and L is monoanion of 4-methylphenylcyanamide (4-Mepcyd) (1), 2,4-dimethylphenylcyanamide (2,4-Me₂pcyd) (2), 3,5-dimethylphenylcyanamide (3,5-Me₂pcyd) (3), 4-methoxyphenylcyanamide (4-MeOpcyd) (4), phenylcyanamide (pcyd) (5), 2-chlorophenylcyanamide (2-Clpcyd) (6), 2,5-dichlorophenylcyanamide (2,5-Cl₂pcyd) (7), 2,6-dichlorophenylcyanamide (2,6-Cl₂pcyd) (8), 4-bromophenylcyanamide (4-Brpcyd) (9), and 2,3,4,5-tetrachlorophenylcyanamide (2,3,4,5-Cl₄pcyd) (10), have been prepared from the reaction of TPPMnCl and thallium salt of related phenylcyanamide. Each of the complexes has been characterized by IR, UV-Vis and ¹H NMR spectroscopies.4-Methylphenylcyanamidotetraphenylporphyrin manganese(III) crystallized with one molecule of solvent CHCl₃ in the triclinic crystal system and space group with the following unit cell parameters of: a = 11.596(6) Å; b = 11.768(9) Å; c = 17.81(2) Å; and α, β, γ are 88.91(9)°, 88.16(7)°, 67.90(5)°, respectively; V = 2251(3) Å³; Z = 2. A total of 4234 reflections with I > 2σ(I) were used to refine the structure to R = 0.0680 and R_w = 0.2297. The Mn(III) shows slightly distorted square pyramidal coordination with the 4-methylphenylcyanamide in the axial position, coordinated from nitrile nitrogen. The reduction of each of the TPPMn-L complexes was also examined in dichloromethane and spectroelectrochemical behavior of (1) was investigated and compared to TPPMnCl.     

The effects of endosulfan on P450 1A gene expression,antioxidant enzymes activity and histopathological alterations in liver of Persian sturgeon (Acipenser persicus Borodin, 1987)

The effects of 14 days exposure to sublethal concentrations of endosulfan (10 and 40 μg L^?1) were investigated in mRNA‐ P450 1A expression, antioxidant enzymes (SOD and CAT) activity and histopathological alterations of Persian sturgeon (Acipenser persicus) fingerlings with weights of 3–5 g. The results illustrated that the relative mRNA‐ P450 1A expression level significantly increased (P < 0.05) compared to the control group. Highest significant increase (P < 0.05) was observed on the first day, then decreased towards day 14 of exposure. The SOD and CAT activity showed a significant increase in fish exposed to different concentrations up to day 7, then activity decreased on day 14 in fish of all treated groups. Although signs of tissue lesions were observed on day 4, they increased from day 7 and reached the highest level on day 14. The magnitude of all changed studied parameters (gene expression, enzymes and histopathological) follows a concentration‐dependent manner.     

Simultaneous chiral separation of tramadol and methadone in tablets,human urine,and plasma by capillary electrophoresis using maltodextrin as the chiral selector

The stereoselective analysis and separation of racemic drugs play an important role in pharmaceutical industry to eliminate the unwanted isomer and find the right therapeutic control for the patient. Present study suggests a maltodextrin‐modified capillary electrophoresis method for a single‐run chiral separation of two closely similar opiate pain relief drugs: tramadol (TRA) and methadone (MET). The best separation method possible for the both enantiomers was achieved on an uncoated fused‐silica capillary at 25°C using 100 mM phosphate buffer (pH 8.0) containing 20% (w v^?1) maltodextrin with dextrose equivalent of 4–7 and an applied voltage of 16 kV. Under optimal conditions, the baseline resolution of TRA and MET enantiomers was obtained in less than 12 minutes. The relative standard deviations (n = 3) of 20 μg mL^?1 TRA and MET were 2.28% and 3.77%, respectively. The detection limits were found to be 2 μg mL^?1 for TRA and 1.5 μg mL^?1 for MET. This method was successfully applied to the measurement of drugs concentration in their tablets, urine, and plasma samples.     

Theoretical investigation of the ring opening process of verdoheme to biliverdin in the presence of dioxygen

The conversion of ferrous verdoheme to ferric biliverdin in the presence of O₂ was investigated using the B3LYP method. Both 6-31G and 6-31G (d) basis sets were employed for geometry optimization calculation as well as energy stabilization estimation. Three possible pathways for the conversion of iron verdoheme to iron biliverdin were considered. In the first route oxygen and reducing electron were employed. In this path formation of ferrous verdoheme-O₂ complex was followed by the addition of one electron to the ferrous-oxycomplex to produce ferric peroxide intermediate. The ferric peroxide intermediate experienced an intramolecular nucleophilic attack to the most positive position at 5-oxo carbons on the ring to form a closed ring biliverdin. Subsequently the ring opening process took place and the iron (III) biliverdin complex was formed. Closed ring iron biliverdin intermediate and open ring iron biliverdin formed as a product of verdoheme cleavage were respectively 13.20 and 32.70 kcal mol⁻¹ more stable than ferric peroxide intermediate. Barrier energy for conversion of ferric peroxide to closed ring Fe (III) biliverdin and from the latter to Fe (III) biliverdin were respectively 8.67 and 3.35 kcal mol⁻¹. In this path spin ground states are doublet except for iron (III) biliverdin in which spin state is quartet. In the second path a ferrous-O₂ complex was formed and, without going to a one electron reduction process, nucleophilic attack of iron superoxide complex took place followed by the formation of iron (III) biliverdin. This path is thermodynamically and kinetically less favorable than the first one. In addition, iron hydro peroxy complex or direct attack of O₂ to macrocycle to form an isoporphyrin type intermediate have shown energy surfaces less favorable than aforementioned routes.     

Clonal hematopoiesis: Genes and underlying mechanisms in cardiovascular disease development

The clonal hematopoiesis when occurring without hematologic abnormalities is defined as clonal hematopoiesis of indeterminate potential (CHIP). Aging causes accumulation of somatic mutations, and hematopoietic stem cells (HSCs) can develop clonal expansion of different lineages by these mutations. CHIP has a correlation with cancer and cardiovascular disease (CVD) through acquired mutations in genes. DNMT3A, TET2, ASXL1, and JAK2 genes as well as other genes are the most common somatic mutations causing CHIP and CVD in an older age. Other factors such as cholesterol level, laboratory tests and indexes also affect CVD. In addition, mutations in adenosine triphosphate–binding cassette transporters and also chronic stress in nervous system can result in HSCs proliferation and CVD. However, laboratory tests and indexes are not sensitive for CVD diagnosis. But the therapeutic interventions can be helpful to prevent CVD cases by targeting somatic mutations, chemokine receptors, and growth factors in HSCs. Also, new drugs can control CVD by targeting of cells and their signaling pathways in HSCs. Therefore, more investigations are needed and more questions should be answered for the relationship between CHIP and CVD as a challenging issue in future.     

Cobalt(II) Schiff base complex on multi-wall carbon nanotubes (MWNTs) by covalently grafted method: Synthesis,characterization and liquid phase epoxidation of cyclohexene by air

Cobalt [(OH)₂-salophen] (N,N′-bis(4-hydroxysalicylidene)phenylene-1,2-diamine) complex was covalently grafted on the chemical modification of multi-wall carbon nanotubes (MWNTs); [Co((OH)₂-salophen)]@MWNTs]. The as-products were characterized by spectroscopy (FT-IR, Raman, and UV–Vis), TGA, and TEM. The cobalt(II) Schiff-base complex covalently anchored on modified MWNTs was characterized by different techniques. The catalytic activity of the novel nanotubes based materials was tested in the epoxidation of cyclohexene in the iso-butyraldehyde/air system using acetonitrile as solvent and very high conversion was obtained. The experimental results indicated very good catalytic activity and selectivity in the epoxidation of cyclohexene. Repeated runs of the catalysts were carried out three times and the results indicated that the catalyst was stable for the epoxidation of cyclohexene.     

The Infrared (Far Terahertz) Generation by Nonlinear Interactions of Two Visible Laser Beams in a Metallic Background: Infrared Surface Plasmon Effect

This paper presents an investigation of infrared (IR) radiation generation by nonlinear interaction of two visible laser beams in a metallic background. Two laser beams of Gaussian and Laguerre Gaussian (LG) profiles and background metals such as silver, copper, gold, and aluminum are utilized for IR generation. Effects of laser beam characteristics and structural properties of metals on the evolution of IR electric field amplitude are examined. Considering laser frequencies in the non-transparent region give rises to generation of IR surface plasmon (IRSP). An optimized relation is proposed for achieving efficient surface plasmon waves on a metal surface.

     

Prevalence of Virulence Genes and Antibiotic Resistance Pattern in Enterococcus Faecalis Isolated from Urinary Tract Infection in Shahrekord,Iran

Background:This study aims to specify the antimicrobial resistance pattern and virulence genes of Enterococcus faecalis isolated from urinary tract infections in Shahrekord, Iran. Methods:Urine samples of 1000 people suspected of having urinary tract infections referred to Shahrekord medical diagnostic laboratories were examined. Biofilm assays were performed by microtiter plate test through reading the OD490. Polymerase Chain Reaction (PCR) was applied to study the virulence factors.Results:Enterococcus faecalis was detected in 60 samples. After performing microbiological tests, all samples were positive in the molecular analysis. Strong, moderate and weak biofilm reactions reported 66.67%, 25%, and 8.33% respectively. The most resistance reported to cotrimoxazole, vancomycin and amikacin and the lowest resistance to nitrofurantoin (8.33%) was reported. Statistical analysis with Fisher''s exact test showed a statistically significant relationship between biofilm production and resistance to cotrimoxazole, vancomycin and cefotaxime. Prevalence of efe A, ace, gel E, esp, cyl M, agg, cyl A and cyl B in strong biofilm formation isolates was reported 100%, 87.5%, 82%, 62.5%, 55%, 37.5% 25% and 22.5% respectively. There was a significant relationship between the frequency of efa A and strong biofilm reaction.Conclusion:The presence of E. faecalis strains resistant to co-trimoxazole and vancomycin and present of some virulence factors is alarming the researchers. Since antibiotic resistance genes are probably transmitted among enterococci, and Staphylococci, controlling infections made by enterococci as well as the appropriate administration of antibiotics could treat the nosocomial infections effectively.Key Words: Antibiotic Resistance, Enterococcus faecalis, Urinary Tract Infection, Virulence genes     

Effects of Sterilization and Temperature on the Decrease Kinetic of Lead Bioavailability in Two Different Soil Groups

Sorption of metal ions by soil and clay minerals is a complex process involving different mechanisms, and controlled by different variables that can interact. The impacts of sterilization and incubation temperature on the decrease kinetic of Pb bioavailability in two different groups of soils were studied. Surface soils were sampled from Guilan and Hamadan provinces in the north and northwest of Iran with temperate and semiarid climates. The decrease kinetic of Pb bioavailability in the Pb(NO₃)₂ treated (400 μg Pb g^?1) soils has been studied in solid state incubation in sterile and unsterile conditions at 15, 27 and 37°C. The decrease of DTPA-extractable Pb in both groups of soils is often characterized by an initial rapid step followed by a slow step. The temperate soil with high affinity surface sites for Pb sorption compared to semiarid soils had a lower DTPA-extractable Pb in each time of extraction. Sterilization and soil incubation at lower temperature decreased the rate of Pb sorption/precipitation processes. Among the kinetic models the second order model and Elovich kinetic equation were the better choice to express the decrease kinetic of Pb bioavailability according to higher determined coefficient and the small standard error of the estimate. The determination coefficients of the mass transfer equation were increased and the standard errors of the estimates were decreased in sterile and unsterile conditions by increasing incubation temperature from 15 to 37°C.