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Mechanistic Investigations of Zinc and Titanium Catalyzed Oxidation, Hydroamination, and Cycloaddition Reactions

Thesis Info

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Author

Nisa, Riffat Un

Supervisor

Khurshid Ayub

Program

PhD

Institute

COMSATS University Islamabad

City

Islamabad

Province

Islamabad.

Country

Pakistan

Thesis Completing Year

2018

Thesis Completion Status

Completed

Subject

Chemistry

Language

English

Link

http://prr.hec.gov.pk/jspui/bitstream/123456789/12486/1/Riffat_un_Nisa_Chemistry_HSR_2018_CIIT_12.09.2018.pdf

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676726630942

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The mechanism of the Zn(II) catalyzed oxidation of benzylic alcohol to benzaldehyde, ester and amide by three different oxidants (H2O2, TBHP, and CH3OOH) is investigated through density functional theory methods and compared with the similar oxidation mechanisms of other late transition metals. Inner sphere, intermediate sphere and outer sphere mechanisms have been analyzed. The effect of pyridine-2- carboxylic acid (ligand) and halides (Br2 and I2) is studied for benzaldehyde and ester formation reactions. Two new reactions are predicted such as oxidation of thiol to thioester and oxidation of benzylamine to benzaldimine and guanidine. The same set of calculations is repeated for newly predicted reactions as were performed for ester and amide formations. The inner sphere mechanism involving β-hydride elimination is found kinetically more demanding in all oxidation reactions. Ligand showed profound effect on rate of the reaction. In the presence of a ligand, intermediate sphere mechanism is found more plausible because of steric effect. In the absence of a ligand, the outer sphere mechanism is found more favorable. Mechanism of Zn(OTf)2 catalyzed hydroamination-hydrogenation of alkynes with amines is investigated through density functional theory methods. Both inner sphere and outer sphere mechanisms for nucleophilic attack of nitrogen on electrophilic alkyne centre to deliver imine have been investigated for the hydroamination reaction. Four different possibilities of hydrogen activation for the hydrogenation of imine to deliver amine have also been studied. These competitive reactions differ regarding the fate of proton and hydride generated from heterolytic cleavage of H2. The inner sphere mechanism is kinetically more demanding and is not believed to contribute significantly to the progress of the reaction under the experimental conditions. Outer sphere route for nucleophilic attack of non-coordinated amine on coordinated alkyne is found the most plausible. The overall energy barrier for outer sphere mechanism in amine adduct can also be surpassed under the reaction conditions, therefore this mechanism cannot be excluded safely. For hydrogenation reaction, heterolytic hydrogen cleavage involving proton shift on triflate ligand and hydride to metal is found most plausible over the competitive H2 cleavage reactions. The mechanism of TiCl4 mediated formal [3 + 3] cyclization of 1,3-bis(silyl enol ethers) with 1,3- dielectrophiles is also studied with B3LYP method of density functional theory (DFT) to rationalize the experimental regioselectivity. Methyl and trifluoromethyl substituted 1,3 dielectrophiles are studied theoretically since they show different regioselectivities. Four different mechanisms involving direct-direct, direct-conjugate, conjugate-direct and conjugate-conjugate addition of 1,3-bis(silyl enol ethers) on 1,3-dielectrophiles are studied for each dienophile. The intramolecular transition metal catalyzed and non-catalyzed dynamic shift of the silyl moiety are also studied. The structure of the 1,3 dienophile and the associated Mulliken charges are the driving forces for different regioselectivities in methyl and trifluoromethyl dienophiles.
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ڈرتے تھے بندوقوں والے ۔۔۔

ڈرتے ہیں بندوقوں والے ایک نہتی لڑکی سے

ڈرتے ہیں بندقوں والے ایک نہتی لڑکی سے

پھیلے ہیں ہمت کے اجالے ایک نہتی لڑکی سے

ملا، تاجر جنرل، جیالے ایک نہتی لڑکی سے

آزادی کی بات نہ کر لوگوں سے نہ مل یہ کہتے ہیں

بے حس، ظالم، دل کے کالے ایک نہتی لڑکی سے

                                                                                                                حبیب جالب

 

Effect of Microwave Power and Time on Total Phenolic Contents and Antioxidant Characteristics of Microwave Assisted Extracts of Watermelon Rind Powder Microwave Assisted Extracts of Watermelon Rind Powder

Watermelon is gaining importance as a functional food due to its therapeutic effect. The therapeutic effect of watermelon has been reported and has been attributed to antioxidant constitutes. The major component in watermelon rind is citrulline that has a strong antioxidant effect which protect body from free-radical damage. Objective: This study was conducted to investigate the effect of microwave powers (150 W, 300 W & 450 W) and time intervals (1, 3 & 5 minutes) on total phenolic content (TPC) and total flavonoid content (TFC) and antioxidant characteristics i.e. DPPH and ferric reducing antioxidant potential (FRAP) of microwave assisted extracts of watermelon rind powder. Methods: The extracts collected after Microwave assisted extraction (MAE) of watermelon rind wereanalyzed for their antioxidant potential through different tests including total phenolic contents (TPC), total flavonoid content (TFC), DPPH assayand FRAP. Results: Microwave assisted extraction by using ethanol as a solvent at different microwave powers and various time intervals showed that total antioxidant potential was significantly higher at low microwave power such as TPC ranges obtained at 150W for 1, 3 & 5 minutes of time intervals show ranges (159.84, 160.04 & 169.71 mg GAE/100 g). While TFC ranges at 150W for time 1, 3 & 5 minutes were (21.31, 24.15 & 42.20 mg CEQ/100g) whereas DPPH ranges at 150W for time 1, 3 & 5 minutes were (53.14, 54.87 & 68.17 % ascorbic acid inhibition) and FRAP values at 150W for time 1, 3 & 5 minutes were (201.71, 221.50 & 326.43 mg FE/100g). While high microwave power 450W can result in disruption of some antioxidants at various time intervals. Conclusions: Watermelon rind is a rich source of many antioxidants andmicrowave assisted extraction technique should be implemented in the food and nutraceutical industries and microwave assisted extracts of watermelon rind should be utilize for the development of new functional food to combat many health related problems

Synthesis and Characterization of Doped and Undoped Metal Oxide Multilayer Thin Films

A variety of multilayer thin films, such as ZnO/TiO2 (ZT), ZnO, TiO2, 1% Cu doped TiO2 (Cu-TiO2), 2% (Cu-TiO2), ZnO/TiO2/ZnO (ZTZ) and TiO2/ZnO/TiO2 (TZT) are deposited by sol-gel technique. In this technique, colloidal particles are dispersed uniformly in a liquid form sol. A gel is a phase in which liquid and solids are dispersed together and form a solid network containing liquid component. The structure, morphology, electrical and optical properties of multilayer films are studied by X-ray Diffractrometer (XRD), Scanning Electron Microscope (SEM), four point probe technique and UV-Vis spectrophotometer, respectively. The properties of the N719 dye sensitized solar cells (DSSCs) of ZTZ and TZT based photoanodes are investigated by current- voltage measurements. XRD patterns of ZT multilayer thin films are confirmed by the presence of all the three phases of TiO2. The average grain size of 1, 3 and 5 stack layers of ZT films is 1.19, 1.22 and 2.56 nm, respectively. Multilayer ZnO films having hexagonal wurtzite structure with average grain size of 1, 3 and 5 layers is 7.96, 11.15 and 17.7 nm, respectively, according to XRD patterns. XRD patterns of TiO2 multilayer films having 1, 2, 3 and 4 stacked layers have shown the anatase phase only with average grain size of 1.06, 1.19, 7.29 and 7.69 nm respectively. Both 1% and 2% Cu doped TiO2 (3, 5 and 7) multilayer films have only the brookite phase of TiO2. The average grain size of 1% Cu doped TiO2 films having 3, 5 and 7 layers is 9.4, 12.9 and 14.4 nm respectively. Similarly, 3, 5 and 7 layers of 2% Cu doped TiO2 thin films have average grain size of 8.85, 14.1 and 14.8 nm respectively. XRD patterns of ZTZ and TZT films have shown anatase phase of TiO2 and cubic phase of ZnO. Average grain size of ZTZ and TZT films is 12.9 and 7.56 nm respectively.Morphology of the multilayer ZT films has shown cracks on the surfaces of 3 and 5 Layers films which may be due to heating and cooling rate of the film. ZnO multilayer films have uniformly distributed grains structures. Both 1% and 2% Cu doped TiO2 multilayer thin films have well defined nano particles with increasing size as the layers increases in SEM micrographs. Both ZTZ and TZT films have densed packed particles due to high viscosity of the sol. Four point probe technique has been used to measure electrical resistivity of films. In all multilayer films, average sheet resistivity is decreased by increasing the layers. The average sheet resistivity of 1, 3 and 5 layers of ZT films is 20.8´ 106,9.12´106 and 7.71´106 ohm-m respectively. The average sheet resistivity of 1, 3 and 5 layers of ZnO thin films is found to be 7.91´105, 5.65´104 and 1.43´104 ohm-m, respectively. For 1, 2, 3 and 4 layers of TiO2 films, the average sheet resistivity is 2.30´107, 1.96´107, 1.41´107, 1.14´107 ohm-m, respectively. The average sheet resistivity for 3, 5 and 7 layers of 1% Cu doped TiO2 films is 8×106, 6.5×106 and 1.0×106 ohm-m, respectively. The average sheet resistivity of 3, 5 and 7 layers of 2% Cu doped TiO2 films is found as “2.19 x 107, 1.20 x 107 and 1.11 x 107 ohm-m” respectively. The average sheet resistivity of ZTZ and TZT films is 9.35 x 104 and 5.44 x 105 ohm-m, respectively. Optical properties of films are measured by UV-Vis spectrometer. The band gap energy (Eg) of ZT having 1, 2 and 3 layers is 3.65 eV, 3.59 eV and 3.53 eV, respectively. The Eg of 1, 3 and 5 layers of ZnO thin films is 3.85, 3.81 and 3.72 eV, respectively. The calculated Eg for 1, 2, 3 and 4 layers of TiO2 thin films is 3.65, 3.60, 3.59 and 3.40 eV, respectively. The Eg of 3, 5 and 7 layers of 1% Cu doped TiO2 films is 3.813, 3.822 and 3.843 eV, respectively. The Eg of 3, 5 and 7 layers of 2% Cu doped TiO2 thin films is 3.778, 3.768 and 3.736 eV, respectively. The calculated Eg of ZTZ and TZT is 3.7 eV and 3.71 eV, respectively.“Due to very low sheet resistivity of ZTZ and TZT thin films as compared to other deposited multilayer films, dye sensitized solar cells of these films are prepared. After deposition, the films are annealed at 450 oC for 30 min and graphene coated FTO glasses are used as counter electrodes. “N719 ruthenium dye is used in these cells and all photovoltaic parameters like open circuit voltage (VOC), short circuit current density (JSC), conversion efficiency (η) and fill factor (FF) are calculated”. X-ray diffraction patterns have shown the presence of both ZnO and TiO2 particles in the films. Morphology of the photoanodes revealed the formation of nanoparticles in both the films; also it has shown that TZT film is more porous and consists of large particles as compared to ZTZ film. Due to this porosity, TZT film absorbed more dye as compared to ZTZ film shown in UV-Vis absorbance graph. The TZT cell has high JSC and VOC as compared to ZTZ cell, resulting high efficiency”.