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Home > Synthesis, Spectroscpic Studies and Reactivity of Chromium 111 Complexes With Aroyl Hydrazines

Synthesis, Spectroscpic Studies and Reactivity of Chromium 111 Complexes With Aroyl Hydrazines

Thesis Info

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Author

Shamshad, Bushra

Program

PhD

Institute

University of Karachi

City

Karachi

Province

Sindh

Country

Pakistan

Thesis Completing Year

2017

Thesis Completion Status

Completed

Subject

Chemistry

Language

English

Link

http://prr.hec.gov.pk/jspui/bitstream/123456789/9858/1/Bushra_Shamshad_Chemistry_HSR_2017_UoK_karachi_18.07.2017.pdf

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676727527272

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Chromium in biological tissues is mostly present in trivalent form and helps to maintain the normal metabolism of glucose, proteins and fats. Literature suggests that chromium(III) complexes have a number of biological activities but some are cytotoxic in nature. So it is necessary to investigate new non-toxic chromium(III) complexes. Aroylhydrazines are biologically important chemical substances and their activities are known to be more improved after complexation with certain metal ions. In order to reveal the chemistry and biochemistry of chromium(III) complexes, the present work explains the synthesis of chromium(III) complexes with aroylhydrazine ligands, their structural and spectroscopic studies. Another significant contribution of this study is the evaluation of the cytotoxic activity, antioxidant nature, antiglycation property and carbonic anhydrase inhibition activities of synthesized chromium(III)-aroylhydrazine complexes. Aroylhydrazine ligands (1-12) with different substituents and their chromium(III) complexes (1a-12a) were synthesized and characterized by using analytical (C, H, N, Cr and Cl- analysis), physical (conductivity measurements) and spectral (EI-Mass, ESI-Mass, FTIR and UV-visible) methods. These physical, analytical and spectral data support that all chromium(III)-aroylhydrazine complexes exhibit an octahedral geometry in which ligand exhibits as a bidentate coordination and two water molecules coordinated at equatorial positions with general formula [Cr(L)2(H2O)2]Cl3. FTIR study demonstrated that in chromium(III)-aroylhydrazine complexes, the ligands were coordinated in a bidentate fashion through carbonyl oxygen and terminal amino nitrogen. ESI-Mass spectra showed that all chromium(III)-aroylhydrazine complexes produce fragments which were assigned to three chlorides and two water molecules from chromium(III) complexes. UV-visible study showed that there are three absorption bands and they also confirmed octahedral geometry of chromium(III)-aroylhydrazine complexes. UV-visible solution study of chromium(III)-aroylhydrazine complexes were evaluated that all of the aroylhydrazine ligands generate stronger ligand field strength than DMSO. Moreover, viii Time dependent stability study of chromium(III)-aroylhydrazine complexes in DMSO showed the decomposition of complex with the passage of time. Some chromium(III) complexes are reported to exhibit cytotoxicity. However, our studies show that chromium(III)-aroylhydrazine complexes reported here were not found to be toxic against normal cells so these compounds were further studied for other biological activities. All chromium(III)-aroylhydrazine complexes were screened for in vitro diphenyl dipicryl hydrazine (DPPH), superoxide dismutase and nitric oxide radical scavenging activities. Majority of the chromium(III)-aroylhydrazine complexes were found to be more effective scavengers as compared to free aroylhydrazine ligands. Studies showed that both steric hindrance and electron inductive effect play an important role in antioxidant activities. Aroylhydrazine ligands and their chromium(III) complexes were also investigated for carbonic anhydrase (CA II) inhibition activity and it was found that all aroylhydrazine ligands were inactive whereas chromium(III)-aroylhydrazine complexes showed excellent carbonic anhydrase inhibition. Chromium(III)-aroylhydrazine complexes with substituents meta position showed higher inhibition potential which may indicate better orientation of these complexes with interactive sites of enzymes. These studies also justified that slight alteration in the structure of the ligands may enhance the biological activities of chromium(III)-aroylhydrazine complexes. Aroylhydrazine ligands and their chromium(III) complexes were also examined for their antiglycation activity in which ligands were found inactive whereas chromium(III)-aroylhydrazine complexes showed significant inhibition of the process of protein glycation. Antiglycation potential of these complexes are dependent upon various factors such as metal-ligand complexation, binding pattern of ligands in the complexes, presence of nitrogen and nature of the ligands. This study provides the opportunity for future researchers to work in this area in order to find more Cr(III)-based antioxidant & antiglycating agents for controlling of diabetes.
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پروفیسر رائز ڈوڈ

پروفیسر رائزڈوڈ

            اسی ماہ میں عالمِ تاریخ کا سب سے بڑا حادثہ پروفیسر رائزڈوڈ کی موت ہے، پروفیسر مرحوم سنسکرت، تاریخِ ہند قدیم اور عہدِ بودھ کے مستند عالم تھے۔ آپ کی zbogogid خاصی دقتِ نظر سے دیکھی جاتی ہے۔ ۱۸۴۷؁ء میں پیدا ہوئے تھے۔

(فروری ۱۹۲۳ء)

 

اسلامی نظام معاشرت میں عدل اجتماعی کی اطلاقی معاشی نوعیت

There is no doubt that the economic system of Islam is stable and compassionate which is based on "Human Amity." This system and its features are utterly beneficial for humanity irrespective of their caste, creed, reigion and religion etc. The specialities of social justice that are applied in the economic field provide such comprehensive and versatile version which makes the utility of the economic system even more pertinent. The humanity can adopt this system to ensure their well-being and welfare.  More importantly, as this system is based on economic justice rather equality, which means, it’s the natural system that depends on human capacities, efforts, innate necessities and abilities. The more a man strives, the more benefit he gets. However, it also sets out the principle of financing those who try hard but stay behind in the economic race. In addition, the fundamental philosophy of this system is to protect the economic rights of the society and provides resources to everyone for equitable economic struggle, with no discrimination. The economic systems around the world suffer from inflation and precariousness, while Social Justice proves to be a remedy to the said scenarios.

Performance of Time Series Models under Structural Discontinuities and Discordant Observations

Existence of outliers and structural breaks whose nature is mutually unknown, in time series data offer challenges to data analysts by causing problems in model identification, estimation and validation. Therefore, the detection of these outliers is an important area of interest in time series. We have investigated outlier detection in time series data using Chen and Liu (1993) and Kaiser and Maravall (2001) methods. We have focused on performance of these procedures in the presence of AO, IO, LS, TC and explored the impact of SLS for the case of SARIMA(p,d,q)(P,D,Q) for p, q=0,1,2; d=0,1; P,Q,D=0,1. The study adds to the literature by critically analyzing the performance of various test statistics for outlier detection under different scenarios using simulation strategy (MCMC) and by collecting empirical evidence from time series data for Pakistan. The evidence is collected by analyzing empirical level of significance, empirical critical values and empirical rejection frequency. We have also explored the confusion between LS, AO and IO, and between SLS and IO, the magnitude of TC that can be ignored and the appropriate critical value (c) for AO, IO, LS, TC and SLS for different sample sizes in various time series models. We also explore the swamping and masking effects of outliers by comparing the Chen and Liu (CL) method with Kaiser and Maravall (2001) procedure for multiple outliers. Our results indicate that the existence of various types of outliers in different time series models generate bias of different nature and is affected by the factors like size of outliers, sample size and cut-off points, and non-normality of the sampling distribution. The simulated empirical critical values are found higher than the theoretical cut-off points, with the empirical level of significance affected by sample size, outlier size and the model parameter coefficients. The empirical power of the test statistics is generally not satisfactory for small sample size, large cut-off points and xviiilarge model coefficient. The empirical analysis is carried out by running the outlier detection procedures on quarterly and monthly measured time series of Pakistan with five possible types of outliers i.e. AO, IO, LS, TC and SLS. The behavior observed for these variables supports our earlier findings. This study has shown that neglecting the SLS may lead to poor statistical analysis as other types of outliers may not fully grasp the impacts caused by SLS. Our simulation analysis does not support the argument of Kaiser and Maravall (2001) of replacing IO by SLS. Application of the method for detecting and removing outliers and structural breaks reduces the residual‟s excess kurtosis, skewness and JB test remarkably. A number of shocks in all series under observation are identified. Amongst which majority are supported by the graphical representation. Existing procedures of outlier detection may provide misspecified results leading to erroneous analysis. Therefore, these identified outliers require support from real world. Finding supportive evidence from real world is done by connecting the indicated discordant observations with historical evidences which may give better understanding. Several „no outlier‟ cases indicate the weakness of adopted procedures. It is concluded that all statistical analysis must include the exercise for outlier detection as it realizes the additional information contained by these aberrant observations, provide insight about policy implementation tools and enable better forecasts. The cut-off point may be set higher to reduce spurious detections. The test statistic for Transient Change should be revisited to have effective identification. Seasonal Level Shift may be included in the list of potential outliers.