Sharifuddin M. Zain

Spatial water quality assessment of Langat River Basin (Malaysia) using environmetric techniques

This study investigates the spatial water quality pattern of seven stations located along the main Langat River. Environmetric methods, namely, the hierarchical agglomerative cluster analysis (HACA), the discriminant analysis (DA), the principal component analysis (PCA), and the factor analysis (FA), were used to study the spatial variations of the most significant water quality variables and to determine the origin of pollution sources. Twenty-three water quality parameters were initially selected and analyzed. Three spatial clusters were formed based on HACA. These clusters are designated as downstream of Langat river, middle stream of Langat river, and upstream of Langat River regions. Forward and backward stepwise DA managed to discriminate six and seven water quality variables, respectively, from the original 23 variables. PCA and FA (varimax functionality) were used to investigate the origin of each water quality variable due to land use activities based on the three clustered regions. Seven principal components (PCs) were obtained with 81% total variation for the high-pollution source (HPS) region, while six PCs with 71% and 79% total variances were obtained for the moderate-pollution source (MPS) and low-pollution source (LPS) regions, respectively. The pollution sources for the HPS and MPS are of anthropogenic sources (industrial, municipal waste, and agricultural runoff). For the LPS region, the domestic and agricultural runoffs are the main sources of pollution. From this study, we can conclude that the application of environmetric methods can reveal meaningful information on the spatial variability of a large and complex river water quality data.

Breakthrough Curve Analysis for Column Dynamics Sorption of Mn(II) Ions from Wastewater by Using Mangostana garcinia Peel-Based Granular-Activated Carbon

The potential of granular-activated carbon (GAC) derived from agrowaste of Mangostene (Mangostana garcinia) fruit peel was investigated in batch and fixed bed system as a replacement of current expensive methods for treating wastewater contaminated by manganese, Mn(II) cations. Batch equilibrium data was analyzed by Langmuir, Freundlich, and Temkin isotherm models at different temperatures. The effect of inlet metal ion concentration (50 mg/L, 70 mg/L, and 100 mg/L), feed flow rate (1 mL/min and 3 mL/min), and activated carbon bed height (4.5 cm and 3 cm) on the breakthrough characteristics of the fixed bed sorption system were determined. The adsorption data were fitted with well-established column models, namely, Thomas, Yoon-Nelson, and Adams-Bohart. The results were best-fitted with Thomas and Yoon-Nelson models rather than Adams-Bohart model for all conditions. The column had been regenerated and reused consecutively for five cycles. The results demonstrated that the prepared activated carbon was suitable for removal of Mn(II) ions from wastewater using batch as well as fixed bed sorption system.

Crystallographic and computational study of 1-(arylamino)-1,2,3-triazole-4-carbohydrazides

The crystallography of mono-p-substituted derivatives of 1-(arylamino)-1,2,3-triazole-4-carbohydrazides, 1 (X = H), 2 (F), 3 (Cl) and 4 (Br), and a 2,5-dichloro (5) analogue, shows the molecular structures to be similar. Distinct hydrogen bonding patterns based on N–H⋯N and N–H⋯O are observed in their crystal structures with 1, having two independent molecules comprising the asymmetric unit, displaying one pattern, 2 and 5 another, and 3 and 4 yet another. Geometry optimisation calculations indicate that any conformational differences in the solid state do not persist in the gas-phase and that no influence of the substituents is seen on the geometric parameters. A natural population analysis, for both experimental and optimised structures, shows that the charge on the triazole-N3 atom is at a maximum for 1, as opposed to 2–5, an observation correlated with its distinctive packing based around a supramolecular synthon not seen in the other structures. For the molecules having electronegative substituents, molecular electrostatic potentials show that the energies of the amine-H4n atoms are reduced for 2 and 5, compared to 3 and 4. A further distinction in 2–5 is indicated by the Hirshfeld surface analysis which highlights the importance of π⋯π interactions in 2 and 5, i.e. with the more electronegative substituents. Clearly, there is interplay between various factors but all correlated with the influence of the electronegativity of the substituent(s).

Preparation and characterizations of activated carbon from kenaf fiber for equilibrium adsorption studies of copper from wastewater

The potential of activated carbon prepared from kenaf fiber (KF) to remove copper (II) from aqueous effluents was investigated. The fibers were first semi-carbonized, then impregnated with potassium hydroxide (KOH) and finally activated by using carbon dioxide (CO2) gas to produce activated carbon. Pore structure and physical characteristics of the prepared kenaf fiber activated carbon (KFAC) were determined. Adsorption studies for divalent copper (Cu) ions were carried out to delineate the effect of contact time, temperature, pH and initial metal ion concentration on equilibrium adsorption capacity. The experimental data followed pseudo-second-order kinetics and Elovich Model than pseudo-first-order. Langmuir, Freundlich and Temkin models were implemented to analyze the parameters for adsorption at 30 °C, 50 °C and 70 °C. Thermodynamic parameters such as ΔGo, ΔHo and ΔSo which represent Gibbs free energy, enthalpy and entropy, respectively, were evaluated. It was concluded that activated carbon from kenaf fiber (KFAC) can be used as an efficient adsorbent for removal of Cu (II) from synthetic wastewater.

Equilibrium Isotherm Modeling, Kinetics and Thermodynamics Study for Removal of Lead from Waste Water

The low cost adsorbent palm oil fuel ash (POFA) derived from an agricultural waste material was investigated as a replacement of current expensive methods for treating wastewater contaminated by Pb(II) cation. Adsorption studies were carried out to delineate the effect of contact time, temperature, pH and initial metal ion concentration. The experimental data followed pseudo second order kinetics which confirms chemisorptions. The values of Langmuir dimensionless constant, RL and Freundlich constant, 1/n were less than 1 representing favorable process for adsorption. Thermodynamic parameters such as ΔG°, ΔH° and ΔS°, related to Gibbs free energy, enthalpy and entropy were evaluated. It was concluded that, chemically treated palm oil fuel ash (POFA) can be used successfully for adsorption of Pb(II) from aqueous solution.

Spatial and temporal air quality pattern recognition using environmetric techniques: a case study in Malaysia

The objective of this study is to identify spatial and temporal patterns in the air quality at three selected Malaysian air monitoring stations based on an eleven-year database (January 2000-December 2010). Four statistical methods, Discriminant Analysis (DA), Hierarchical Agglomerative Cluster Analysis (HACA), Principal Component Analysis (PCA) and Artificial Neural Networks (ANNs), were selected to analyze the datasets of five air quality parameters, namely: SO2, NO2, O3, CO and particulate matter with a diameter size of below 10 μm (PM10). The three selected air monitoring stations share the characteristic of being located in highly urbanized areas and are surrounded by a number of industries. The DA results show that spatial characterizations allow successful discrimination between the three stations, while HACA shows the temporal pattern from the monthly and yearly factor analysis which correlates with severe haze episodes that have happened in this country at certain periods of time. The PCA results show that the major source of air pollution is mostly due to the combustion of fossil fuel in motor vehicles and industrial activities. The spatial pattern recognition (S-ANN) results show a better prediction performance in discriminating between the regions, with an excellent percentage of correct classification compared to DA. This study presents the necessity and usefulness of environmetric techniques for the interpretation of large datasets aiming to obtain better information about air quality patterns based on spatial and temporal characterizations at the selected air monitoring stations.

Electronic structures of carbazole and its derivatives: A Semi-empirical study on the substitution effects of carbazole.

The electronic structures of carbazole, N-phenylcarbazole (NPC), cyanophenylcarbazole (CPC) and N-ethylcarbazole (NEC) have been calculated using the quantum chemical semi-empirical MINDO/3 method. In this paper, electronic ground states and first singlet excited states of the systems mentioned were investigated. It is observed that the excitation energy of carbazole based on the calculated difference in heats of formation agrees quite well with experimental data obtained from supersonic expansion studies. Calculated energy levels of molecular orbitals and their graphical forms are used qualitatively in elucidating the S0 → S1 excitation electronic origin red shifts observed in carbazole derivatives with respect to the electronic origin of the parent carbazole. It is noted that the red shifts are not just a result of the destabilization of the HOMO of carbazole but are also determined by the nature of the substituting moieties. It is also observed that the LUMO of CPC is not derived from the parent carbazole which partially explains the difference in electronic behaviour as compared with the other derivatives.

Laser-induced fluorescence spectroscopy of jet-cooled phenylcarbazole and a weakly bonded carbazole—benzene complex

Abstract Laser-induced fluorescence (LIF) excitation spectra of phenylcarbazole and a weakly bonded carbazole—benzene complex are presented. A prominent long progression with up to 7 quanta transitions was assigned to the intermolecular bending vibration β in the complex between the carbazole and benzene moieties. Bands corresponding to up to 6 quanta transitions with a similar but slightly weaker intensity profile distribution to β was found to arise from the “hot band” of the complex. The LIF excitation spectrum of phenylcarbazole resembles closely that of carbazole and the cyanophenylcarbazole chromophores. The emission spectrum following the excitation of the origin is a good mirror image of that of the excitation, and results in little or no change of geometry of the molecule on going from the ground state to the electronically excited state. The two aromatic ring planes in phenylcarbazole are orthogonal to each other with C 2v symmetry. The emission spectra following excitation of other vibronic modes with up to 800 cm −1 excess energy above S 1 are presented.

Validation of quantitative structure-activity relationship (QSAR) model for photosensitizer activity prediction.

Photodynamic therapy is a relatively new treatment method for cancer which utilizes a combination of oxygen, a photosensitizer and light to generate reactive singlet oxygen that eradicates tumors via direct cell-killing, vasculature damage and engagement of the immune system. Most of photosensitizers that are in clinical and pre-clinical assessments, or those that are already approved for clinical use, are mainly based on cyclic tetrapyrroles. In an attempt to discover new effective photosensitizers, we report the use of the quantitative structure-activity relationship (QSAR) method to develop a model that could correlate the structural features of cyclic tetrapyrrole-based compounds with their photodynamic therapy (PDT) activity. In this study, a set of 36 porphyrin derivatives was used in the model development where 24 of these compounds were in the training set and the remaining 12 compounds were in the test set. The development of the QSAR model involved the use of the multiple linear regression analysis (MLRA) method. Based on the method, r2 value, r2 (CV) value and r2 prediction value of 0.87, 0.71 and 0.70 were obtained. The QSAR model was also employed to predict the experimental compounds in an external test set. This external test set comprises 20 porphyrin-based compounds with experimental IC50 values ranging from 0.39 μM to 7.04 μM. Thus the model showed good correlative and predictive ability, with a predictive correlation coefficient (r2 prediction for external test set) of 0.52. The developed QSAR model was used to discover some compounds as new lead photosensitizers from this external test set.

A STRUCTURAL STUDY OF THE INTERACTION OF DIBENZYLDIAZA-18-CROWN-6 WITH NEODYMIUM(III) NITRATE HEXAHYDRATE

Abstract The structure of the complex salt, [C26H40N2O4][Nd(NO3)5(H2O)] (1), was determined by single crystal X-ray diffraction. It consists of alternating layers of the anionic complex, [Nd(NO3)5(H2O)]2−, and the cationic diprotonated [2H.azacrown]2+. The Nd3+ complex anion is coordinated to five bidentate nitrate ligands and a water ligand to give an 11-coordinated environment. Each Nd moiety is linked to another through intermolecular hydrogen bonding to form pairs of Nd moieties. The azacrown adopts a chair conformation and the benzyl groups are attached to the nitrogen atoms in an anti position with respect to each other, above and below the plane of the macro-ring in agreement with the conformation of the uncomplexed protonated azacrown as obtained by the PM3 method.