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Home > Synthesis Characterization and Biological Sciences of Some Novel Schiff Base Derivatives of Ferrocence and Their Metal Complexes

Synthesis Characterization and Biological Sciences of Some Novel Schiff Base Derivatives of Ferrocence and Their Metal Complexes

Thesis Info

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Author

Jawaria, Rifat

Program

PhD

Institute

Bahauddin Zakariya University

City

Multan

Province

KPK

Country

Pakistan

Thesis Completing Year

2016

Thesis Completion Status

Completed

Subject

Chemistry

Language

English

Link

http://prr.hec.gov.pk/jspui/bitstream/123456789/10436/1/Rifat_Jawaria_Chemistry_2016_BZU_Multan_HSR_04.10.2017.pdf

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676727476828

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Focus of this research work is on the synthesis and biological studies of ferrocenyl thiosemicarbazones and their transition metal complexes. Two series of Schiff’s base derivatives of acetylferrocene (58-71 & 87-101) were synthesized by the condensation of acetylferrocene with appropriate benzylthiosemicarbazides (44-57) and phenylthiosemicarbazides (72-86) in ethanol under the catalysis of acetic acid. All these compounds were fully characterized by IR, 1H NMR, 13CNMR spectroscopic and EIMS spectrometric data. Crystallographically studies of ferrocene-based thiosemicarbazones have been conducted in order to investigate the prevalence of the thioamide dimersynthon and carbon bonding. All the compounds have shown a general preference for the adoption of the cis, trans conformation about the central thiourea moiety which is ideal for the formation of a dimeric hydrogen-bonded {···H–N–C=S}2 synthon as the building block. This dimeric synthon is observed in all the compounds, with the methyl group particularly set for playing its supportive stabilization role through C-H···S and carbon bonding interactions. The structural features and ground state geometry calculations have been computed at B3LYP/6- 31G** (LANL2DZ) level of theory. The computed geometrical parameters, bond lengths, bond angles and dihedral angles are in reasonable agreement with the X-ray crystallographic data. We shed light on the frontier molecular orbitals; highest occupied molecular orbitals (HOMOs), lowest unoccupied molecular orbitals (LUMOs) and HOMO-LUMO energy gaps. The intra-molecular charge transfer (ICT) was observed in all the studied compounds. The excited state geometries have been optimized by using the time-dependent DFT. Metal complexes of benzylthiosemicarbazones (102-127) were prepared by reacting with metal salts (CuCl2, CoCl2, Zn(acetate)2 and Ni(acetate)2) with benzylthiosemicarbazones in 1 : 2 ratio respectively. All the complexes were characterized by IR, UV-Vis, Molar conductance and Magnetic moment. Crystal structure of Co(II) (120) complexe was grown and characterized to confirm the structure and geometry of metal complexes. The crystallographic data confirmed the tetrahedral geometry of synthesized metal complexes. The synthesized thiosemicarbazones and their metal complexes (58-127) were tested against acetylcholenesterase (AChE), butyrylcholinesterase (BChE), alpha glucosidase, lipoxygenase (LOX) and antioxidant activities. In general, all newly synthesized metal complexes (102- 127) showed higher inhibitory activities than their respective ligands. The Cu(II) complex (102) was found to be the most potent against acetylcholenesterase as well as butyrylcholenesterase having IC50 values 9.21±0.29 μM and 12.70±0.27μM respectively while its ligand was in active. For alpha glucosidase activity, the metal complex (106) was highly active with IC50 value 0.8±0.19μM (%inhibition= 99.92±0.21) while its respective ligand did not show considerable activity (% inhibition 15.71±0.66). Similar behavior was observed for lipoxygenase (LOX) enzyme where compound (122) was most active (IC50 = 15.02±0.0 μM, % inhibition = 93.58±1.21) while its ligand was inactive. The Co(II) complex (121) showed moderate DPPH radical scavenging activity with % inhibition of 83.74±0.96 (IC50 = 169.67±0.75μM). High biological activities of metal complexes as compared to their respective ligands highlighted the importance of complexation. The studies show the importance of new class of thiosemicarbazones and their metal complexes that enhanced their biological interest.
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زبان اللہ تعالیٰ کی ایک عظیم نعمت ہے۔ یہ اظہار کا ذریعہ ہے۔ صوتیات وہ علم ہے جو ہمیں زبان کی آوازوں اور ان کی جان کاری میں نہ صرف مدد فراہم کرتا ہے، بل کہ اس کے لیے اصول بھی مرتب کرتا ہے۔ صوتیات میں زبان کی آوازوں کےپیداہونے کے طریقے اور ان کی صحیح درجہ بندی کا مطالعہ کیاجاتا ہے۔ صوتیات لسانیات کی اہم شاخ ہے۔ بعض علمائے لسانیات کے بقول صوتیات کے بغیر لسانیات نا کافی ہے۔ صوتیات کا کام زبان کی آوازوں کو دریافت کرنا، اس کو صحیح رسم الخط فراہم کرنا، جن زبانوں کے پاس رسم الخط نہیں ہے انہیں رسم الخط فراہم کرنا اور الفاظ کی درست ادائیگی میں معاونت ہے۔ ہر زبان میں عہد کے ساتھ ساتھ تبدیلیاں رونماہوتی رہتی ہیں۔کچھ الفاظ متروک ہوتےہیں، کچھ کا املا بدل جاتا ہے اور کچھ قواعد واصول بھی بدلتے رہتےہیں۔ صوتیات کسی بھی زبان کا منظم علامتی اور تصوراتی نظام ہوتا ہے۔ انسانی ذہن بے شمار آوازیں پیدا کرنے کی خُداداد صلاحیت رکھتا ہے۔ انسانی منہ سے اَن گنت آوازیں نکلتی ہیں لیکن صوتیات میں صرف بامعنی آوازوں کا مطالعہ کیا جاتا ہے۔ زمان ومکان کے حالات کے مطابق زبان میں پایا جانے والا تغیر وتبدل اس کی صوتی ہیئت میں بھی تبدیلیاں لاتا ہے۔
صوتیات کی تعریف
بقول پروفیسر اقتدار حسین:
’’زبان کی آوازوں کے سائینٹی فک یامنظم طور سے مطالعے کو صوتیات کہتے ہیں۔‘‘۲۹؎
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Discovery Learning Effect on Mathemathic Learning

This study aimed to improve the mathematics learning through the application of the Discovery Learning model with a scientific approach. The application of the Discovery Learning learning model with an effective scientific approach can increase the frequency of activeness and activities in the teaching and learning process according to the observations of student attitudes during the implementation of classroom action research. It showed that Student learning outcomes that are not entirely satisfactory are also caused by several factors, namely individual student factors, student environment and school environment.

Analysis of the Potential of Non-Pathogen Derived Resistance Against Begomoviruses

Cotton leaf curl disease (CLCuD) is the major threat to cotton crop and is transmitted by whitefly (Bemisia tabaci). Whitefly is also a major pest of cotton crop and significantly damages the crop worldwide. Whitefly bears endosymbionts which live inside gut of insect and endosymbionts produces some protein which may be essential for different metabolic processes. There are some primary endosymbionts which are present in almost all whitefly biotypes but the presence of secondary endosymbionts is dependent on its biotype, ecological distribution and some other unknown factors. These endosymbionts produce a protein GroEL which helps in transmission of cotton leaf curl disease which is a begomoviral disease. There may be co-localization of two or more than two secondary endosymbionts in the same whitefly. The presence of endosymbionts such as Hamiltonella, Rickettsia, Wolbachia, Fritschea, Cardinium and Arsenophonus were tested in whiteflies collected from cotton growing areas of Pakistan and several combinations of endosymbionts were found. Similarly, GroEL gene was cloned and its relationship with already known GroEL was established. Two approaches were used here: these are the control of whitefly through RNAi technology and the expression of GroEL in transgenic plants to generate broad-spectrum resistance. Two RNAi target genes trehalase and trehalose transporter were selected on the basis of their involvement in important physiological pathways in whiteflies. The osmotic pressure of the phloem sap is about five times higher as compared to that in the insect gut. The difference in osmotic pressure forces the fluid to move from phloem into the insect’s gut where it also poses major challenge for the phloem feeders to normalize the pressure by degrading the sucrose content of the phloem sap. Trehalase is present in all tissues and is involved in trehalose transporter metabolism that is it hydrolyzes trehalose transporter into two glucose molecules. In insect trehalase is also found to play important role in functions like flight metabolism, chitin synthesis during molting and cold tolerance. Trehalose transporter is a non-reducing sugar also known as α- D-glucopyranosyl α – D glucopyranoside and is a disaccharide of glucose. Phenotypic manifestation of gene knockdown by dsRNA induced RNAi suggested lowered expression of target genes. Real time qPCR was xv performed in order to estimate transcript levels and the results from expression profiling of whiteflies treated with dsRNA to induce RNAi against the specific targets showed significant success in knocking down expression of the target genes. Bioassays conducted for the target genes showed high mortality rates for dsRNA treated whiteflies, suggesting that the gene knockdown could be an effective way for controlling insect pests like whiteflies. Since multiple begomoviruses and associated satellites are involved in CLCuD, approaches based on the concept of broad-spectrum resistance are essential for effective disease control. GroEL and G5 are two proteins from whitefly endosymbiont and M13 bacteriophage origin respectively. GroEL encapsulates the virus particle when it enters the whitefly and protects the virus from immune system of whitefly as well as prevents viral expression in it. This characteristic of GroEL can be exploited to get resistance against viruses if expressed in plants. G5 is a single stranded DNA binding protein, expression of which in transgenic plants will stop viral expression on its binding with ssDNA. Use of tissue specific promoter is more efficient than constitutive promoters. NSP of BBTV is phloem specific promoter using which, GroEL can be expressed only in phloem tissues, the site for viral entry. To attain broad spectrum resistance, pyramiding of both genes was done. Transgenics of Nicotiana benthamiana for GroEL under constitutive promoter, GroEL under phloem specific promoter, gene pyramid of GroEL and G5 both with their constitutive promoters and gene pyramid of GroEL and G5 in which GroEL under phloem specific and G5 under constitutive promoter were made. In comparison to non-transgenic plants, transgenic plants with double cassette of GroEL under NSP promoter and G5 under 35S promoter showed promising results when challenged against Cotton leaf curl Multan virus (CLCuMuV) along with Cotton leaf curl Multan betasatellite (CLCuMB), Cotton leaf curl Khokhran virus (CLCuKoV) along with Cotton leaf curl Multan betasatellite (CLCuMB) and Pedilenthus leaf curl virus (PedLCV) along with Tobacco leaf curl betasatellite (TbLCB). The data presented here shows that RNAi technology can be effectively used for controlling whiteflies while the expression of GroEL under phloem-specific promoter could be an effective way achieve broad-spectrum resistance.