Iraqi National Journal Of Chemistry

AbstractThis paper concerned with development of a spectrophotometric method for the determination of trace amounts of Benzocaine, based on the diazotisation and coupling reaction with acetyl acetone in basic medium, to form an intense yellow coloured, water-soluble and stable azo-dye which shows a maximum absorption at 419.5nm. Beer’s law is obeyed over the concentration range of 0.04-12 µg/ml, with molar absorptivity of 25000 l.mol-1.cm-1 and Sandell’s sensitivity index of 6.6×10-3µg.cm-2, relative error of -3.80 to +3.95% and relative standard deviation of ± 0.013to ±0.32%. The method has been applied successfully for the determination of benzocaine in two synthetic pharmaceutical formulation.

AbstractThe drug cyclophosphamid CP has harmful genetic effects when used with higher doses. For this reason, this study was carried out to determine these harmful effects, and try to reduce these effects by using the metabolic extract of green tea. The extract was characterized using TLC .The results indicate that the extract contained various compounds. Rats were treated with different doses of CP and DNA extracted from WBC and analyses with DNA electrophoresis. The results showed that there was a direct relationship between the dose of CP and level of DNA lysis. The results also showed that giving the green tea extract before the CP is the best way in reducing the effects of CP on DNA. These results may indicate that the extract works as antimutagenic agent, while when given with the CP , the extract may works as desmutagenic agent. The MI results showed that treating the rats with CP alone reduced MI (23.33), when compared with the negative control (39.33) .When the extract was given before the CP, MI was (34.33), while the MI was (30.66) and (25.66) when the extract was given with and after the CP, respectively. Chromosomal studied in bone marrow cell of rats indicate that the CP at 20 mg / Kg causes increase in the level of chromosomal aberrations. These aberrations increase and decrease in the number of chromosomes, ring chromosome, brakes in the chromosomes and chromatiedes and in the centromere region, and other aberrations. However when the green tea extract was given before or with the CP the level of chromosomal aberrations was reduced in comparison with the positive control. From the results of present study, we conclude that the green tea extract had antimutagenic effect when given at the dose of 1 g / Kg before and with the CP.

Abstract The extensive utilization of hydrophobic organic compounds such as surfactants generates high environmental pollution levels. Due to their hydrophobicity, this type of compound tends to accumulate in soil organic matter. Distribution coefficient (Kd), Freundlich adsorption coefficient (Kf) and Langmuir adsorption coefficient (KL¬) for adsorption of Triton X-100 on three agricultural soil samples with different characteristics were determined. Adsorption of Triton X-100 in solutions was best fitted to the Freundlich equation.The effects of soil organic matter (OM) content, soil clay content and exchangeable cation content of natural soils on the adsorption capacity of Triton X-100 in water-solid systems were investigated based on the adsorption isotherm analysis. Results showed that, values of Kd and Kf increased with increasing soil OM content, but varied irregularly with clay content, exchangeable cations and pH.

Abstract Extraction of Cu+2ions from aqueous solutions reagent 2-[(4-chloro -2-methoxyphenyl)azo]-4,5 diphenylimidazole (4-ClMePADPAI) shows the optimum conditions for extraction was (pHex=8) ,concentration of Cu+2ions in aqueous solution (30μg) (9.45×10-5M),as well as shaking time (10 min) ,all these conditions giving higher distribution ratio (D) ,organic solvent effect shows there is not any linear relation between distribution ratio (D) and dielectric constant (ε),for organic solvents used but there is an the effect for organic solvent structure on the extraction method .Stoichiometric study shows the more probable structure of ion pair complex extracted for Cu+2ions with reagent (4-ClMePADPAI) was1:1 (metal:reagent)[Cu(4-ClMePADPAI)]+2SO4-2. The effect of temperature on the extraction of Cu+2ions shows the reaction between Cu+2ions reagent ((4-ClMePADPAI) was exothermic

Abstract A simple, sensitive and selective method has been developed for the determinations of 2-aminophenol and catechol. The method is based on the reaction of 2-aminophenol and catechol with p-aminoacetophenone and dichromate at pH 5 and 4.5 were Studied. The reactions gave and an intense water soluble color products their have a maximum absorption at 506.5 , 540 nm and εmax 0.3*104 and 0.7*104 for 2-aminophenol and catechol respectively .A linear correlations (1-9 μgml-1) for both compounds were found between absorbance at λmax and concentration. The results obtained are both precise (RSD were better than 1.9 % and 2.2 % respectively) and accurate (relative error were better than 0.47% and 0.25%) . The colored products were found to be 1:1 2-aminophenol : p-aminoacetophenon and catechol : p-aminoacetophenon . The stability constants and the rate constants of the reactions under optimized conditions and at room temperature were 5*104 L.mole-1, 3.46*10-2 min-1 and 3*106 L.mole -1 , 1.39*10-2 min-1 respectively.

Abstract The direct and catalytic photodegradations of toxic and widely used herbicide, 2-methyl-4-chlorophenoxyacetic acid (MCPA) were investigated under the artificial (UV and Visible) and solar source of radiation, in aqueous suspensions of TiO2 and ZnO. UV-Visible spectroscopy and High performance Liquid Chromatography (HPLC) were used to monitor changes of herbicides concentration.The degradation of MCPA in all experiments followed a pseudo-first order reaction .The reaction rate constants of the processes for UV/ TiO2 system was 0.369 min-1 and for UV/ZnO system was 0.0171 min-1. The effect of the initial herbicide concentration was investigated and was concluded that the rate of herbicide degradation can be described in terms of Langmuir-Hinshelwood kinetic model.

AbstractA new spectrophotometric method has been developed for the determination of trace amounts of Salicylidene – 3, 4 – dimethyl aniline (I) via coupling with sulfanilic acid sodium salt at pH =7.2 . The method is simple, precise and selective for the determination of enol contents of in a range 1.65 to 3.47 ppm. The study is extended to study a tautomerism reaction of type enol  keto in molecule (I), beside the thermodynamic study of such reaction in solution state. The results show the enol content in molecule (I), is predominant as evident from the positive value of average ΔG function of value 1.552kJ. mol-1. Moreover, other calculated ΔH and ΔS parametrs have an avarage negative values of about – 9.016 kJ. mol-1 and –33.765 J. mol-1. K-1 respectively, these support the tautomerism reaction.

Abstract The results of measurements of excess molar volumes VE at 298.15 K over the whole mole fraction range for five mixtures (N-methylmorpholine + 2-pentanol; + 3-pentanol;+ 3-methyl-1-butanol; + 2-methyl-1-butanol; and 2-methyl-2-butanol) are presented. The experimental values of VE show a negative deviation from ideal for the five sets of binary mixtures in except VE values for mixtures of (N-methylmorpholine + 2-pentanol; and 3-pentanol) showes two structural regions. The first is positive at mole fraction 0≤X2≥0.25. The second region is negative at mole fraction 0.25≤X2≥1. The negativity of VE increases in the order 2-methyl-2-butanol > 2-methyl-1-butanol > 3-methyl-1-butanol > 3-pentanol > 2-pentanol. The experimental results of VE are compared with those predicted by the Prigogine- Flory- Petterson theory . The theory poorly predicts the experimental VE. The experimental value of excess molar volumes VE were fitted to the Redlich- Kister polynomial equation to derive the binary adjustable parameters and the standard deviations. The results obtained are used to study the nature of molecular interactions in these mixtures. As far as we know, in the open literature, no study on mixtures containing N-methylmorpholine

Abstract Photocatalytic disinfection reaction under UV- visible light in presence of oxygen and Titanium dioxide (TiO2) in aqueous solution has been investigated .This method is effective for killing Escherichia -coli bacteria in water. TiO2 semiconductor exhibits strong bacterial activity .The aim of this research is to design a new photobioreactor and its application to sterilize the water from E-coli bacteria .Primary experiments have been done to determined the optimum conditions which lead to high killing efficiency of E-coli bacteria in aqueous solution . The results showed that the bacterial effect of TiO2 under UV-visible light irradiation on E-coli bacterial suspension was much higher than without using TiO2 .The photocatalytic reactions were carried out with various TiO2 concentrations. The highest photocatalytic E-coli photokilling rate was obtained at 0.5 mg/ml TiO2 concentration ,which is equal to 3.25 x 10-2 CFUs /sec .This rate was increased to 5.8 x10-2 CFUs /sec when 10 ppm of hydrogen peroxide was add to E-coli aqueous solution under UV- visible light in presence of oxygen and ideal concentration of TiO2 (0.5mg/ml). The mechanism of TiO2 illumination to produce oxidizing species and the effect of these species on the bacterial activity in aqueous solution has been suggested.

Abstract Two series of N3 Schiff base complexes [M L1 Cl] and 22-membered hexaazamacrocyclic complexes [ML2] (M=Co2+, Ni2+, and Cu2+) have been synthesised via the condensation reaction of para-nitobenzaldehyde with diethelyenetriammine to obtain [HL1] where [HL1]= N-[(4-nitrophenyl)methylene]-N'-(2-{[(4-nitrophenyl)methylene]amino}ethyl)ethane-1,2-diamine and diethylene triammine with 2,5hexane dione to from [HL2] where [HL2] = 8,11,19,22-Tetramethyl-1,4,7,12,15,18hexaaza-cyclodocosa-7,11,18,22-tetraene, in the presence of acetic acid as a catalyst in ethanol. The prepared compounds were haracterized by FT- IR, 1H-NMR, and electronic spectral studies, conductivity, elemental microanalysis and magnetic moment measurements The mode of bonding and overall geometry of the complexes have been inferred through IR, and electronic spectral studies, conductivity, and magnetic moment measurements.[ Co Cl L1] is distorted tetrahedral, [Ni Cl3 L1] is octahedral, and [Cu Cl L1] is square planar, An octahedral geometry is proposed for [Co L2] and [Ni L2] complexes and square planar for [Cu L2].

Abstract This paper presents the synthesis and study of some new mixed-liagnd complexes containing tow amino acids[Alanine(Ala) and phenylalanine (phe)] with some metals .The results products were found to be solid crystalline complexes which have been characterized by using (FT-IR,UV-Vis) spectra , melting point, elemental analysis (C.H.N) , molar conductivity and solubiltyThe proposed structure of the complexes using program , chem office 3D(2000) .The general formula have been given for the prepared complexes :[M(A-H)(phe-H)]M(II): Hg , Mn ,Co , Ni , Cu ) , Zn , Cd(II) .Ala = Alanine acid = C3H7NO2Phe = phenylalanine = C9H11NO2

AbstractThe present investigation involves the synthesis of new Co(II), Ni(II) and Cu(II) complexes from reaction Co(II), Ni(II) and Cu(II) chlorides with two terpyridines. One of the ligands act as tridentate and the other act as bidentate. All the prepared complexes were characterized by their metal analyses, IR and UV-vis spectroscopy, conductivity, magnetic measurements and theoretical study. Conductivity data in DMSO showed that some complexes are 1:2 (M:L) electrolytes which assigning the formula [M(L1)2(H2O)2]Cl2 while the other complexes are non-electrolyte which assigning the formula [M2(L2)2Cl4]. Electronic spectral data and magnetic measurements showed that some of the complexes have octahedral geometry while the other complexes have tetrahedral geometry.

Abstract This study was carried out to assess further the association between cigarette smoking and the accompanied alterations in lipid profile. Forty smokers and thirty non smokers were included in our study; all volunteers were males of comparable ages. The enzymatic methods were employed to determine the concentrations of total cholesterol, triglycerides, high-density lipoprotein, low-density lipoprotein and very low-density lipoprotein. The mean levels of total cholesterol, triglycerides and very low-density lipoprotein were significantly increased in smokers when compared to non smokers exhibiting a direct dose response relationship. Only insignificant elevation was noticed in the mean level of low-density lipoprotein. The anti atherogenic high-density lipoproteins mean level was significantly lower in smokers than in non smokers. Risk ratios were calculated as TC/HDL-C, LDL-C/ HDL-C and non- HDL-C/ HDL-C and were observed to be significantly higher in smokers than in non smokers. These findings confirm and extend those of various studies in other countries. The observed alterations in lipid profile in smokers along with high risk ratios do indicate that smoking produces adverse effects on lipid profile, therefore increasing the atherosclerotic disease risk.

AbstractSafe doses of low-intensive visible, class (II) He-Ne laser of λ= 632.8 nm in a dose response of (12-84) J/cm2 has been used for investigating laser effects on thyroid gland function of rabbits. Thyroid gland function was examined by monitoring and determining the triiodothyronine (T3), thyroxin (T4) and the thyroid stimulating hormone TSH level before (as controls) and after laser irradiation. The activity of Thyroid Glad for (T3) and (T4) production increase directly with laser exposure duration while the rate of TSH production decreases by the same rate.The correlation of T3, T4 and the TSH hormones production during laser irradiation also studied con-firing our data is the closely correlated that obtained for three hormones investigated.

Abstract Spectroscopic studies in the U.V region were carried out on human PSA. The U.V spectra of PSA, was obtained and revealed that PSA have a characteristic spectrum. The effect of pH and polarity on PSA U.V spectra was studied. Spectrophotometric pH titration and solvent perturbation were carried out and the data revealed that about 83.3% of tyrosine residues are located on the surface of the PSA molecule, while about 16.7% of tyrosine residues are buried interior the folded structure of the PSA. About 27.4% of histidine residues is located on the surface of the PSA molecule, while about 72.6% of histidine residues is embedded in the interior region of the PSA molecule.

Abstract Human milk is the first food human encounter and it serves as the sole source of all nutrients required for the biological functions and growth during the early stages of life. Trace elements contents are therefore of importance from nutritional point of view. Moreover, accurate data on the concentrations of trace elements in human milk throughout early lactation are important for developing milk formula substitutes. Raw milk as it comes from cow is the natural substitute to human milk for infant feeding. However, overdose of these mineral constituents can be harmful. This study was directed to measure the concentrations of Zinc (Zn), Cadmium (Cd), Chromium (Cr), Copper (Cu) cobalt (Co), nickel (Ni), iron (Fe) and manganese (Mn) in human, animal, commercial fresh cow milk samples available in Erbil city. A total of 30 human milk samples, 10 animal milk samples (cow and goat) and 27 commercial fresh cow milk samples were analyzed after wet digestion for the eight trace elements using Atomic Absorption Spectrometer. The mean values of contents (in ppb) of these elements in breast milk obtained from mothers 1~3 days postpartum were 2.47, 6.56, 18.93, 5.04, 564.29, 1163.47, 302.15 and 6.94, respectively. While those in animal milk were 3.375, 7.75, 14.5, 28, 300.5, 1012.5, 183 and 4.23, respectively. And those in commercial fresh cow milk were 4.51, 9.044, 19.55, 17.65, 395.09, 841.211, 35.72 and 6.95, respectively. The mean concentrations of these elements in breast milk comparable with values of WHO/IAEA study.

Abstract This study is conducted to determination the serum level of sialic acid(SA),Alkaline phosphatase ALP, Lactate dehydrogenase LDH and Creatine kinase(CK) in 25 patients with colon cancer, 25 patients with rectal cancer and 25 healthy subjects. Serum SA, ALP and LDH levels in patients with colon and rectal cancer were significantly higher than control groups and serum CK level in patients with colon and rectal cancer was nonsignificantly higher than control. There were a positive significant correlation between SA and ALP and LDH but there was a positive nonsignificant correlation between SA and CK. The results suggest that the alteration of SA, ALP and LDH levels were related to the pathogenesis of colorectal cancer.

AbstractThis study was included 22 rabbits induced diabetes mellitus disease (DM) by injection the alloxan under skin, and then evaluation the activity of creatine kinase and antioxidants of blood serum and white blood cells (WBCs),(glutathione and, uric acid) with lipid peroxidants (malondialdehyde). Before starting the evaluation, it was prepared the (WBCs) and serum from the rabbits 22 control.The results of the study showed that there are significantly increased in level of MDA (µmol/L) in serum of rabbits with DM 1.68 0.42 ±,±1.54 0.43 for (WBCs) compared with controls 0.83 ±0.29, 0.77 ± 0.26 in both serum and (WBCs), respectively and significantly decreased in activity of creatine kinase in patients for serum 80.622± IU/L compared with controls 105.538± IU/L (P ≤ 0.01) in both serum and, (WBCs) also significantly decreased in the level of the glutathione and uric acid in patients 16.3 ± 6.4, 144.6 ± 42 μmol/L compared with controls 26.7± 10.3, 240.3 ± 41 μmol/L , (P ≤ 0.01) in both serum and, (WBCs). Finally, this study was not found significant differences between the levels of serum and (WBCs) in each groups of rabbits for all the parameters studied (creatine kinase, glutathione, uric acid and malondialdehyde.

Abstract Total prostate specific antigen (t-PSA) levels were measured in sera and tissues of three groups of patients with breast tumors using immunoradiometric assay (IRMA). Group I consisted of 29 women suffering from benign breast tumors. Group II and III consisted of 21 and 27 women suffering from pre- and postmenopausal malignant breast tumors. In addition to that, another group of 32 women were used as control. The results obtained revealed that the levels of serum t-PSA in group I was increased significantly (P< 0.0001) whereas in group II and III, the levels of serum t-PSA were slightly significant (P< 0.05). An immunoradiometric assay procedure was developed for the determination of t-PSA in the three groups. Total PSA (t-PSA) level in tissues of patients with group I was significantly higher than in group II and III (p< 0.001) whereas the level of t-PSA in tissues of patients with group II and III were no significant (P< 0.1). The results obtained revealed higher incidence of t-PSA in group I than those in group II and III.

AbstractNaturally occurring auxin (IAA) was measured spectrophotometrically as indicator for oxidative processes that occurs during ageing phenomenon, in terms of rooting response of mung bean cuttings.According to oxidative hypothesis fresh and aged cuttings as well as stock plants were supplied with nutrient solutions that are associated with anti-oxidant defense mechanisms, to investigate their effects in suppression of oxidative stress that accompanied aging phenomenon. The data revealed the followings:-a)A decline in rooting response of aged cuttings (held in d/H2O for 3 days) were taken from seedlings grown in Hoagland solution compared to fresh cuttings, with a percentage of decline equal to 11.8% in presence of NAA, 10-4 M and 30.8% in its absence. This coincided with the decline of IAA level in aged cuttings compared to fresh cuttings, and was attributed to oxidative processes that occurs during ageing.b)A decline in rooting response of aged cuttings in d/H2O (supplied with auxin) taken from seedlings grown in Hoagland solutions lacking for B or Fe, compared to control(complete Hoagland solution).c)Significant increase in rooting response of cuttings aged in d/H2O (not supplied with auxin) taken from seedlings grown in Hoagland solution lacking for Mn or B.d)Increase in rooting response of fresh cuttings treated with low concentration of SeO2 (0.001-10 ppm).e)Increase in rooting response of cuttings aged in different strengths of complete, modified nutrient solution (CMNS), except the case of CMNS (SeO2=1 ppm). This confirmed the role of selenium as anti-oxidant in defense mechanisms occurring in cuttings during ageing.f)Increase in rootings response of cuttings aged in d/H2O (not supplied with auxin), taken from seedlings grown in CMNS lacking for boron ( In this case, B substituted by Se). g)Decrease in rooting response of cuttings taken from seedlings grown in d/H2O for (10) days, and aged in CMNS (Half strength) lacking for Mn or group of elements (Mn, Zn, and Se). The discussion was focused on the importance of trace elements in their resistance to the damage that resulted by oxidative processes, occurring during aging.