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Development of Organic Linkers and Functionalized Metal Coordination Complexes: An Industrial Nose

Thesis Info

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Author

Mansab, Saira

Program

PhD

Institute

Fatima Jinnah Women University

City

Rawalpindi

Province

Punjab

Country

Pakistan

Thesis Completing Year

2019

Thesis Completion Status

Completed

Subject

Environmental Sciences

Language

English

Link

http://prr.hec.gov.pk/jspui/bitstream/123456789/12573/1/PhD%20thesis%20Red%20print.pdf

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676724621769

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Currently, the scientists are directing their research in finding solutions for the risks associated with unanticipated and undetected chemical pollutants. The major efforts are focused on early identification and investigation of pollution issues before they worsen the environment and human health. In this aspect, new metal coordination complexes are explored as most sustainable materials. The efficiency can be tailor-made in terms of surface area, pore volume and conjugation of ligands for diverse sensing and remedial applications. The present research was aimed to synthesize single and mixed ligand coordination complexes based on nitrogen containing ligands (imidazole, triazole, pyridyl) with understanding that nitrogen has a significant role in binding with organic moiety. A series of coordination complexes were synthesized where both ligands were coordinated with zinc followed by post-synthesis modification for incorporation of amine groups. The assessment of structural surface and bulk properties was undertaken with a range of analytical techniques. Results of 1H-NMR identified structural modifications due to functionalization induced by amine moiety. The optimum (72% and 76%) incorporation was obtained for ethyl amine in imidazole and triazole, respectively. Further, binding of primary and secondary ligands in different ratios developed unique structures for mixed ligand coordination complexes. Another characteristic of complexes was binding of functional groups at amine position indicated by disappearance of distinctive (3000-3400cm-1) peak in FTIR analysis. The significance of the synthesized materials was their high structural and thermal stability due to metal coordination. However, incorporation of larger amine groups resulted in decrease in surface area. The synthesized single ligand and conjugated complexes were tested for adsorption and sensing potential against herbicide and nitro compounds, respectively. The highest (79%) adsorption efficiency was monitored for (Zn(NH-TBA)2Eth(NH2)2), due to maximum number of amine groups. The well-known adsorption isotherms and kinetics equation suggested that process pre-dominantly followed physio-sorption mechanism sequentially from sub-monolayer to multi-layered structure. Intra-particle model expressed three phase diffusion, via external surface, micropores and mesopores of the materials. The chemical sensing potential of conjugated (mixed ligand) complexes was determined through Photoluminescence studies. A blue shift with optimum intensity was recorded for complexes in comparison to ligand depicting the significant sensing for nitro compounds. Further, maximum quenching efficiency was noted for 4,4''- dibenzohydrazobenzene and nitroaniline, proposing collisional and static quenching mechanism. The electrical conductance of synthesized complexes was explored using impedance. An important aspect revealed was the charge transfer and diffusion resistance and radius of semicircle of Nyquist shifted to higher frequency due to increase in heterogeneity. These results were elaborated further by Randles-Ershler equivalent circuit model. The research submitted encouraging results opening a wide application window for the synthesized single-ligand and conjugated coordination complexes. The novelty of functionalization in complexes was also offered. The study testified the potential and efficacy as adsorbents, biosensors and semiconductors. The study concludes that these materials offer great capacity for commercial viability and suitable candidate for environmental remediation and luminescence-sensing applications.
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غلام احمد فرقت

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عالمی امن میں اسلام کا کردار

We live in a global village. The cyber world has brought together people and shurnk the distences, yet multi cultural, multi ethinic and multi national has become the norm of the day. There is virtually no such place, no town, no village, city or state where people from diverse backgrounds speaking diffirent lagnuages and professing diffirent creeds live. This diveristy and variety is the essence of life.  This paper analyzes various ways of establishing peace in the light of Islamic teachings. It finds out the causes of quarrels and disputes in different nations so that they may be prevented to make the world peaceful.

Optical Emission Spectroscopy of N2-H2-Natural Ch4 Mixture Plasmas Generated by Pulsed-Dc for Surface Hardening of Austenitic Stainless Steel

Nitrogen glow discharge plasma is generated by number of power sources and has many applications in material processing such as Nitriding of different metal alloys. The material processing efficiency of the plasma may be enhanced by optimizing the related parameters of the discharge. The concentration of the active nitrogen species in the plasma may depend on various operating conditions such as input power of the discharge, pressure and gas flow rate etc. In order to improve the various excitation and ionization processes occurring in the plasma for the generation of active species, one way is to mix some inert gas in the nitrogen plasma. In the present study the diagnostics of Pulsed-dc generated nitrogen-methane-hydrogen mixture plasma is carried out to analyze the optimum working conditions for its application. Spectroscopic measurements of hydrogen Balmer-β and Balmer-γ line profiles are performed in an abnormal glow region of Pulsed-dc sustained nitrogen-hydrogen- methane plasma for investigating dependencies of their line shapes and intensities on discharge parameters. The excitation temperature Te is determined from Ar-I emission line intensities by using Boltzmann’s plot method of Balmer lines is found to be increased with methane mixing in nitrogen plasma. The electron density is extracted from Stark broadening (FWHM) of the Hβ emission profile. It is found that both the emission intensity and the broadening of the Balmer-β and Balmer-γ lines show significant dependence on the filling pressure in the same manner. However, both the emission intensity and broadening of Hβ line exhibit weak dependence on input power in contrast to the Hγ emission line. The concentration of active species N 2 (C 3 P u ) + + and N 2 ( B 2 S u ) are monitored in terms of the emission intensities of nitrogen bands of the second positive and the first negative systems respectively. The concentration of N 2 (C 3 P u ) active species is appreciably enhanced by methane mixing signifying the role of argon meta-stables in the excitation and dissociation processes. The effect of mixing of methane-hydrogen is studied on the surface nitriding os AISI-304 stainless steel substrate at temperature of 500 0C generated by 50 Hz pulsing source at powers of 300 and 500 watt and filling pressure of 1, 3, 5 mbar at different treated times 1, 2, 3, 4 and 5 hours. The samples are then analyzed for plasma induced changes in their surface properties by using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and Vicker’s micro hardness testing. The XRD pattern confirms the formation of expanded austenite phase (γN) resulted by the incorporation of nitrogen as interstitial solid solution in the iron lattice. The EDX spectra show peaks corresponding to elements that are present in the surface of the substrate. It can be noticed that no additional peak corresponding to any impurity element, other than nitrogen, which is supposed to be present owing to nitrogen incorporation in the iron lattice is found in EDX spectra. The effect of ion etching is apparent from the SEM micrograph, which is normally expected during the nitriding process. All the nitrided samples show an increase in surface hardness as compared to that of untreated one. It is revealed that the surface hardness increase significantly with increasing nitriding time. Based upon optical measurement reported here, plasma discharge parameters can be optimized for the production of active species, excitation temperature Te and number density.