Research Journal of Chemistry and Environment

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Vol. 12(4) December 2008

UV Photochemical Degradation of a Phenyl-Urea Herbicide Chlorotoluron

Klementova Sarka* and Zemanova Martina

UV photochemical degradation of chlorotoluron was shown to be a photolytic process non-influenced by the presence of environmentally important catalyst (ferric ions) or sensitizers (soil humic isolate and humic peatbog wate), independent of pH values in the range from 2 to 11, with F = 0.008. Reaction proceeds via chloride ions release and hydroxyderivative formation. Significant extent of mineralization was observed (20% of C in 90 min. of irradiation). Reaction rate depends on a solvent, reaction rate constant in water, water : methanol = 95:5 (v/v) and methanol being 0.065 min-1, 0.036 min-1 and 0.12 min-1 resp. In the highly absorbing humic water samples, degradation through the interaction with HO• radicals is suggested.

Effect Of Environmental Factors (Temperature and Humidity) on Spinning Worms of Silkworm (Bombyx mori L.)

Ghosh Manisankar*, Mukhopadhyay Ujjal and Mukhopadhyay Aniruddha

After taking different scientific measures during silkworm rearing for harvesting successful cocoon crop and for the production of good quality raw silk, cocoon growers are loosing their crops with traditional mounting system and environmental conditions. It is observed that high and low temperature and humidity conditions during larval spinning influence greatly on cocoon and silk production. To asses the post effect of cocoon formation and raw silk production on M12 (w) and Nistari (M) races, the present study was undertaken. Just after completion of fifth instar rearing, spinning larvae of both the races were collected and mounted on bamboo made chandrikes. Chandrikes were kept in three different small chambers of different environment containing high (28 ±1 0C temperature and 90 ± 2 %R.H), medium (23 ±1 0C temperature and 75 ± 2%R.H), and low (18 ±1 0C temperature and 60 ± 2%R.H) temperature and humidity respectively. Different cocoon and silk characters like single cocoon wt., shell wt., S.R%, filament length, renditta, denier etc. were recorded and analysed. Both the races show inferior quality cocoons and silk filament with high melting percentage at high temperature and humidity. Spinning of worms at low temperature and humidity did not show significant difference with the control. So it is clear from this experiment that temperature and humidity of environment have direct effect on silk spinning and reeling performance.

HS-SPME and SD Extraction and Analysis of Volatile Oil in Tridaxprocumbens.L by GC/MS

Xu Runsheng, Liu Yanhui and Yuan Ke*

In this study,the essential oils were extracted from Tridaxprocumbens.L by Headspace-solid-phase microextraction (HS-SPME) technique and steam distillation(SD). The chemical constituents of essential oils separated were identified by GC/MS analysis, the relative content of the constituents from the essential oils were determined by area normalization method. There were 43 constituents which were separated and identified by Headspace-solid-phase micro-extraction, which accounted for over 99.59% of total essential oil fraction. There were 58 constituents which were separated and identified by steam distillation, which accounted for over 98.74% of total essential oil fraction. Headspace-solid-phase microextraction technique has the advantages of fast extraction speed, It is simple, inexpensive and solvent-free. HS-SPME integrates extraction clean-up,concentration and GC injection ioto a single step when compared with steam distillation method. HS-SPME is a powerful tool for determining the volatile constituents present in the TCMs.

Synthesis and Characterization of Some new Alkoxyphthalimide Derivatives of Benzimidozolylthiazolidinones

Bapna Archita, Sain Devendra Kumar and Talesara G. L.*

Reaction of o-phenylenediamine and p-aminobenzoic acid in 1N HCl afforded 2-(4-aminophenyl)-1H-benzimidazole (1), which readily underwent condensation reaction with benzaldehyde to yield schif’s base (2). Cyclization of (2) by refluxing with mercaptoacetic acid in DMF furnished 3-[4-(1H-benzimidazol-2-yl)phenyl]-2-phenyl-1,3-thiazolidin-4-one (3). Compound (3) on treatment with various aromatic aldehydes gave corresponding arylidene derivatives (4a-d). Subsequently compounds (4a-d) were converted to corresponding 3-[4-(1H-benzimidazol-2-yl)phenyl]-1-N-ethoxyphthalimido-5-(arylidene)-2-phenyl-1,3-thiazolidin-4-one (5a-d) by treatment with phthalimidoxyethyl bromide. The structures of synthesized compounds have been assigned on the basis of elemental analysis and spectral data.

Solution State Studies on Thermodynamic Parameters, Mechanism of Protonation and Complex Formation of Binary Complexes of La(III), Ce(III), Pr(III) and Nd(III) with Aminopyridines

Sharma Sangita,* Shah Mayur C., Dalwadi Dipika, Thakkar Falguni and Vora J.J.

The determination of formation constants and thermodynamic parameters (DG, DH and DS) of binary Lanthonen(III) complexes (ML), where M = La (III) or Ce (III) or Pr (III) or Nd (III) and L = 2-aminopyridine or 3-aminopyridine or 4-aminopyridine have been carried out using Irving – Rossotti titration technique in aqueous media at different temperatures and at different ionic strengths. The formation constant (log bn) have been calculated on IBM computer using least square methods. The Smin values are also calculated. The metal ligand formation constant values of selected aminopyridine were in the order 4-aminopyridine > 2-aminopyridine > 3-aminopyridine. The order of stability for metals is La < Ce < Pr < Nd. These orders can be explained on the basis of basicity of ligand, protonation of ligand, electronic configuration of metal ions, size and ionic potential of tripositive ion, charge/size ratio of metal ions and species distribution diagrams. The mechanism through which protonation and complex formation takes place have been also discussed and shown by chemical reactions. Species distribution curves of complexes have been plotted as function of pH using Fortran IV programs to visualize their equilibria system. To understand more about the nature of equilibria involving lanthanide(III) complexes with aminopyridines, the effect of dielectric constants on the stability of these complexes at different percentage of solvent variation and at different solvent systems has been studied.

Use of HQSAR for the development of a Molecular model of 2-hydroxyl-3-alkyl-1,4-naphthoquinones as Photosystem II Inhibitors

Ding Feng, Song Wenhua* and Gao Minling

2-hydroxyl-3-alkyl-1,4-naphthoquinones are inhibitors of photosystem II. Quantitative structure-activity relationship (QSAR) was studied using the hologram QSAR (HQSAR) method. Two models having the cross-validated regression coefficient of 0.704, 0.717 proved to be the best two. The models consisted of the alignments of atoms+donors and acceptors, atoms+bonds+connections respectively. These models were optimized by changing the fragment distinction and size. The HQSAR models had a greater predictive ability than models derived from the traditional 2D-QSAR approach. Base on these models, 2-hydroxyl-3-alkyl-1,4-naphtho-quinones could compete with QB via a hydrogen bond or other intermolecular forces to combine with D1; blocking the electron transfer process of plant photosynthesis. The analysis of the contribution maps was found to be in good agreement with the proposed inhibition mechanism of 2-hydroxyl-3-alkyl-1,4-naphthoquinones.

Swelling and Mechanical Properties of Genipin Cross-linked Chitosan/Poly(ethylene glycol) Hydrogel Network

Dagbay Kevin B.* and Jalando-on Katherine P.

Chitosan isolated from black tiger prawn shrimp (Penaeus monodon) was characterized based on its average molecular weight using viscometry and degree of deacetylation from its FTIR spectra. Low molecular weight poly(ethylene oxide) and a cross-linker (genipin) were blended with chitosan to improve its physical and mechanical properties. Tensile strength and percentage elongation at break, stability in water and swelling capacity of the films in phosphate saline buffer at 37oC were investigated. Results showed that the blue-colored cross-linked blend films had better mechanical properties, more stable in water and swell more in acidic media than in neutral solution, as compared with the light yellow uncross-linked blend films. FTIR analysis showed H-bonding interactions in the chitosan/genipin/PEO blend. SEM reveals considerable surface morphological changes where chitosan/PEO and chitosan/genipin/PEO exhibit roughness at the polymer surface. Cross-linked chitosan hydrogel showed initial surface deposition of hydroxycarbonate apatite (HCA) upon immersion in simulated body fluid (BSF).These desirable physico-biochemical properties of chitosan-based hydrogel films indicate a potential for biomedical applications.

Assessment of Methane Emission from Municipal Solid Wastes Disposal Sites

Akolkar A. B.*, Choudhury M. K. and Selvi P. K.

Assessment of landfill gases (LFG) with appropriate methodology for control of green house gas emission as well as possibility for waste to energy conversion are the prime objectives of the study. Generation of LFG from a particular heap of wastes can not be interlinked with the potential of LFG generation. Rather, LFG emission depends on the spatial /physical conditions like anaerobic condition, depth from surface, age of dumping and chemical compositions like carbohydrate and protein contents in the waste.

Concentrations of Nitrate and Nitrite in Groundwater Resources of Hamadan Province, Iran

Jahed Khaniki Gh. R.*, Dehghani M.H., Mahvi A.H., Rafati L. and Tavanafar F.

Nitrate and nitrite are naturally occurring ions that are ubiquitous in the environment. Both are products of the oxidation of nitrogen by microorganisms in plants, soil or water. After a period of time, the nitrates seep into the water table. Nitrates produce no color and no odor in water and can cause cancer in humans, when consumed over a long period of time. The objective of this study was to investigate and determine the nitrate and nitrite compounds in groundwater resources of Hamadan province, Iran. Totally 280 samples of water were examined for nitrate and nitrite during a period of six months from February to September, 2007 belonging to eight cities of Hamadan Province (Hamadan, Malayer, Nahavand, Asadabad, Razan, Bahar, Kabudarahang and Toyserkan). Nitrate and nitrite ions were both analyzed by a UV- Spectrophotometer, DR- 5000. Results showed that the mean and standard deviation of nitrate and nitrite concentrations in water samples were 16.39 ± 14.05 mg/l and 0.038 ± 0.056 mg/l respectively. Nitrate for ten samples of water from five cities (Malayer, Razan, Bahar, Kabudarahang and Toyserkan) had been more than the maximum acceptable concentration (MAC) in drinking water. It was concluded that nitrate content in drinking water was often higher than the standard level in some areas and thus it can be a public health concern for people who consume this contaminated water. Source water protection should be important at these areas and it is also necessary to apply few additional actions to reduce or remove nitrate from drinking water.

Sodium Chloride as an Estimation Indicator of Ground Waters Pollutant Load from Land Surfaces of Coastal Karst

Milena Tadić* and Stanka Filipović

In order to estimate ground waters pollutant load from land surfaces of coastal karstic basin, some ingredients of water, such as mol ratio of Na/Cl as permanent ingredients of wastewaters, have been used as indicators in this paper. For example, it has been chosen the karstic basin where the wastewaters of a smaller town, without previous purification, flow into karstic pothole and after certain retention in the underground appear at the spring of the watercourse, which feeds the waters of Lake Skadar as final recipient of these and other waters from powerful basin1, significantly influenced for a long period by the artificial factor2,3,4. The data provided by the indicator role of mol ratio between major cations and some anions of water prove previous statement. The pollution of karstic underground is demonstrated with high sodium and chlorides load values of pothole waters (T0), which has affected the quality of spring waters (T1). During an annual investigation, when the period of small waters prevailed, 840 “temporary” samples taken from the pothole (T0) and spring (T1) have been sampled and analysed. Apart from the scientific knowledge the obtained data are estimated to have great importance in defining and taking necessary measures for water protection of the basin in question, which is a precondition for already defined strategy of Montenegrin’s state development.

Synthesis, Spectroscopic Characterisation and Antimicrobial Activity of Metal Complexes with Quadridentate Schiff Base

Rubavathy Jaya Priya A., Rajavel R.* and Prasad S.

The Schiff base complexes are formed newly using different transition metals at their stable oxidation state as Copper(II), Nickel(II) and Oxovanadium(IV). 2-hydroxy-1-napthaldehyde, 4,5 dichloro-orthophenelynediamine and salicylal-dehyde were condensed to form a new unsymmetrical Schiff base ligand having an azomethine group responsible for better chelating to the metal center. Authenticities of the ligand and their complexes have been established by IR, electronic, conductivity and cyclic voltammetry. The antimicrobial activity of the monobasic tetradentate Schiff base ligand and its complexes against the microbes such as Bacillus subtilis, Staphylococcus aureus, Klebsiella pneumoniae and Escherichia coli have been carried out using Muller Hinton Agar as medium. All of these complexes showed significant activities than the free ligand.

Synthesis of N-[5-(guanidinopentyl)-N-[3-[(3-methyl-1-oxo-2 butenyl) amino] propyldodecanamide

Walwil Abdalla M.

Scheme 1 is the proposed synthesis of the fatty acyl amide, compound (1). The starting material 5-aminopentanol (2) can be converted to (3) through the conjugate addition of the substrate acrylonitrile. Alkanoylation, Friedel-Crafts Acylation, of the secondary amine produces (4). Reduction of (4) using the lithium aluminum hydride - cobaltous chloride mixture gives (5). Acylation of (5) by 3,3-dimethylacryloyl chloride yields (6). Tosylation of the primary alcohol(6) affords (7) which can be guanidinylated to produce (1).

Migration and total Concentration of Heavy Metals in Soil Samples from the Zeta Valley, Montenegro

Blagojevic N.Z.*, Vukasinovic-Pesic V.L. and Djurovic D.D.

The total and the migration concentration of lead (Pb), cadmium (Cd), copper (Cu), zinc (Zn), iron (Fe) and manganese (Mn) in 20 soil samples taken from the surrounding area of Aluminium Factory Podgorica, airports, asphalt plant and highroad in Zeta Valley (Montenegro) were determined. The applied method for preparation of soil samples was the extraction method using CH3COONH4 and CH3COOH for migration concentration, and HCl for total concentration of metals. The concentrations of examined metals were determined by flame atomic absorption spectrometry (FAAS) method. The migration concentration of Pb, Cd and Zn in investigated soil samples ranged within the values allowed by the regulations, the concentrations of migration of Fe and Mn were in accordance to the natural concentration and the migration concentration of Cu in two samples exceeded allowable limits. The total concentration of metals in particular soil samples exceeded the values allowed by the regulations, which is probably the consequence of the influence of aluminium factory, street traffic and usage of plant protection products.

Reactions of Hexabutylditin with Tertiary Amines

Bansal Deepika, Manmohan and Mittal R.K.*

The reactions of hexabutylditin with tertiary amine in molar ratios of 1:2 were studied in the medium of anhydrous chloroform or benzene. Complexes of the type [R3Sn]2.2NR3 (where R= Et, Bu and Ph) have been synthesized. In these reactions it was observed that two molecules of the ligand form adducts. The resulting adducts were obtained in the form of yellow liquid or grey solid. They are soluble in common organic solvents. The conductivity measurements do not support their ionic nature. These adducts appear to be five coordinated and structure may be trigonal bipyramidal.

Synthesis and characterization of complexes of Manganese (II) with 2-(Furan-2-formylimino)benzimidazole

Jose C. V.* and Anto T. Joy

Complexes of Mn(II) with 2-(Furan-2-formylimino)benzimidazole have been synthesized. Characterization has been done on the basis of elemental analysis, conductivity measurements, magnetic studies, IR and electronic spectral studies. Complexes has been found psychopharmaco-logically more effective in taming, hypnotic activities and possess much higher toxicity as compared to the ligand. Complexes with distorted octahedral geometry with ML2X2 stoichiometries have been reported (where x=cl, NO3 , CH3COO & C6H5COO).

Photo-oxidative Degradation and Quantification of Herbicide Residues for Pesticidal Pollution

Gupta Sandhya and Kushwaha S.S.S.*

A highly selective and sensitive chromato-graphic technique in combination with electro-chemical as well as photo-active detection has been developed to identify and determine trace levels of phenoxy herbicides, such as; 2,4-dichloro-phenoxyacetic acid (2,4-D); 2,4,5-trichloro-phenoxyacetic acid (2,4,5-T); 4-chloro-2-methylphenoxyacetic acid (MCPA); 2-(2,4-dichlorophenoxy) propionic acid (2,4-DP); 4-(2,4-dichlorophenoxy)butyric acid (MCPB) and 4-(3,4-dichlorophenoxy)butyric acid (2,4-DB). Also, the photo-oxidation of hazardous herbicides by strong oxidizing agent hydrogen peroxide in the presence of UV radiations is also investigated. The UV + H2O2 combination generates hydroxyl radicals having very high oxidation potential which helps in complete mineralization of a herbicide. The photo-oxidation process is found to be strongly pH dependent. The electochemical behaviour of these six herbi-cides is found to be different which is due to the varying number of chlorine atoms in the aromatic moiety and the different aliphatic side chains. It is observed that UV irradiation increases selectivity as well as sensitivity of the electrochemical reaction. Further, the photo-oxidative degradation by UV + H2O2 combination is found to cause complete mineralization of herbicide pollutants. The rate of this process is directly proportional to intensity of UV radiations and pH of the medium. Also, a mathematical model on kinetics of degradation of herbicides is developed so as to estimate herbicide residues in soil and vegetation as a function of time for different orders of herbicide decomposition reactions. This may help to understand the fate of environmental pollution caused by herbicide applications.

In-situ Transesterification of Non-edible Oil from Thespesia Poulnea Seeds

Pokharkar Raghunath D., Dalvi Sanjaykumar, Funde Prasad E. and Pingale Shirish S.*

A new non-edible oil source to obtain biodiesel from in-situ transesterification reaction of Thespesia poulnea seeds of kernels has been studied. The seeds are found to contain non-edible oil in the range of 73%. In this paper the aim is to produce biodiesel directly from seeds by in-situ transesterification reaction. One can demonstrate the cost effective new source of energy by single step reaction. i.e. production of oil by combining extraction and reaction of extract with the mixture of alcohols to obtain oil as one of the best in-situ transesterification.

Mini Review: Green Cluster Ethyl cyanoacetate – A versatile reagent

Kale Mrunali S.

Ethyl cyanoacetate is widely used as an active methylene reagent in variety of conden-sation reactions. It also plays a very important role in organic synthesis as well as in medicinal chemistry due to ease formation of C-C bond formations reactions.