Metal complexes exhibit a wide variety of functional groups in drug designing and development due their vaious chemical properties, coordination modes, geometries and reactivities. Organonikellated and silver complexes have become attractive tool in the field of catalytic as well as medicinal chemistry. The present project was designed to synthesize new series of silver-N-Heterocyclic carbene (NHC) and cyclonickellated complexes. Various NHC based as well as phosphine/phosphinite based precursors were designed leading to the synthesis of target silver and nickel complexes, respectively. Three series (A-C) of novel mono- and bisimidazolium salts (1a-16a, 1b-12b, 1c-7c) as ligands and their mono, di, tri and polynuclear silver complexes (17a-20a, 13b-20b, 8c-12c) were synthesized. The corresponding silver(I) aducts were afforded by the in situ deprotonation of the NHC based ligands. Some of the NHC salts (7a-12a) of series A were found to be difficult to react with silver due to steric factor (bulky alkyl substituents attached to them), so their silver complexes could not be synthesized. The synthetic approaches of the ligands of series B were controlled by the methyl substituents attached to the backbone of benzimidazole imposing significant impact on the reactivity by the virtue of their aptitude to enhance sigma electron donating ability of ligands. The precursors and silver complexes were well characterized by FTIR, GC-MS, 1H, 13C (one and two dimensional), 31P and 19F NMR, elemental analysis, melting points, ESI-MS and single crystal X-ray crystallographic techniques. Adopting a different protocol of synthesis using excess of reactant, an interesting trinuclear silvercomplex (8c) was synthesized. After successful syntheses, the silver complexes were employed to study their redox potentials by cyclic voltammetry. The quasi reversibility and irreversibility of redox events in the electrochemical study of silver complexes indicated that the reduction event produces unstable decomposed species and oxidation event may be ascribed to decomposed species. Azolium salts and their Ag(I)-NHC complexes were tested in vitro against Bacillus subtillis, Macrococcus brunensis, and Bacillus cereus to study their antibacterial activity and against MDA-MB-231 and HCT116 cells to study their anticancer potential. All compounds were observed to pose potential antibacterial and anticancer activity, however, silver-NHC complexes were found relatively more potent compared to the corresponding NHC precursors (salts). Only few salts were found inactive, while their complexes were observed to be active concluding that the silver imparts greater anticancer potential to the compounds. Being air and moisture sensitive, cyclonickellated complexes could not be utilized for evaluation of their antimicrobial, anticancer or redox potential, however, the attempts were made to study their functionalization behaviour under inert atmosphere. It was observed that the coordination of PR2 moiety into CNi bond is apparent from the initial colour change and shift of 31P NMR and 19F NMR signals but final products of insertion remained difficult to be analyzed as they usually decomposed or appeared NMR silent after workup.In order to understand the feasibility of reaction and to evaluate the properties of product of insertion, further attempts were made to get target complexes via different way by synthesizing phosphine-phosphinite ligands and reacting them with nickel precursor. Appearance of specific signals in NMR spectra of few products provided some evidences of formation of the target products but later the products decomposed and signals disappeared. Thus the products of all reactions were very difficult to identify by NMR either due to paramagnetic nature or decomposition of products and crystallization attempts remained unsuccessful so their structures remained ambiguous as no other technique could help to study them due to their air/moisture sensitivity. On the whole the present project provided useful information for drug designing and chemical transformation studies.
الرئیس جمال عبدالناصرمرحوم صدر ناصر جمال عبدالناصر دنیا کے ان عظیم المرتبت لوگوں میں سے تھے جواپنے بلند اور عظیم کارناموں کے باعث تاریخ میں اپنے لیے ایک مقام ہی پیدا نہیں کرتے بلکہ تاریخ کوایک نیا موڑ بھی دیتے ہیں ا ور اسی بناء پر ان کی شخصیت محض ایک تاریخی نہیں بلکہ تاریخ ساز شخصیت ہوتی ہے۔ انھوں نے ۵۲ء میں برسر ِاقتدار آکر اپنے ملک کوشہنشاہیت کی زنجیروں سے آزاد کیا اورعوام کامعیار زندگی اونچا کیا۔۵۶ء میں نہر سویز کوقومیالینا اور کروڑوں روپے کے خرچ سے اسوان ڈیم کی تعمیر کردینا مرحوم کے دو ایسے عظیم کارنامے ہیں جنھوں نے اقتصادی اعتبار سے مصر کی تقدیر بدل دی ہے۔اس کے علاوہ انھوں نے ملک میں زرعی،زمینی تعلیمی اور اقتصادی اصلاحات بھی نافذ کیں اورصنعت وحرفت کوفروغ دیا اور پھرخود ان کی زندگی نہایت سادہ عوامی اوراخلاقی اعتبارسے بہت بلند تھی۔ان سب چیزوں نے مصر کے عوام کوان کاایسا گرویدہ بنادیا تھاکہ ۶۷ء کی جنگ میں شدید شکست کے بعد جب انھوں نے ساری ذمہ داری اپنے سر لے کر حکومت کی صدارت سے استعفا پیش کیا تو عوام ایک پر جنون کی کیفیت طاری ہوگئی اورآخر انھیں استعفا واپس لیناپڑا۔ مرحوم صرف اپنے ملک کے نہیں بلکہ پوری عرب دنیا اور افریقی اقوام کے بھی سب سے زیادہ قابل اعتماد، نہایت فعال اور بڑے جرّی اور ہوش مند لیڈر تھے۔ان میں سے بعض ملکوں کے سر براہوں کی سیاست خواہ کچھ ہی ہو لیکن عوام ہرملک کے صرف ان کی عزّت ہی نہیں کرتے تھے، بلکہ دل وجان سے محبّت کرتے تھے۔چنانچہ ان کی اچانک اور بے وقت موت پر کروڑوں انسانوں نے بے ساختہ جوگریۂ وماتم کیاہے وہ تاریخ میں کم ہی لوگوں کونصیب ہوا ہوگا۔ غلطیوں اورفروگزاشتوں سے کوئی فرد بشر خالی نہیں ہے اور پھرجو شخص جتنا بڑا ہوتا ہے اس...
The acceptance of new students (PPDB) using the zoning system was first implemented in Yogyakarta in 2018/2019. This zoning system aims to equalize education and improve the quality of education. This research was conducted to find out how the zoning system policy in Yogyakarta city under the auspices of the Yogyakarta City Education Office. This research uses qualitative approach with case study method. The results of the study showed that the zoning system in Yogyakarta has changed from the previous year. In 2019/2020 the zoning system provides a 10% chance of superior seeds, 30% of school zones, 10% of poor learners, 40% of quality pathways, 5% of out-of-school zoning pathways, and 5% of special pathways such as prospective learners whose parents moved from other regions to Yogyakarta. With this zoning system, the whole community has the opportunity to get a good quality education.
Due to availability of powerful image editing tools images are open to several manipulations. Therefore, their authenticity is becoming questionable especially when images have influential power, for example in a court of law, news reports, insurance claims, criminal investigation, medical imaging etc. The most common image tampering often for malicious purposes is to copy a region and paste to hide some other region of the same image is known as copy-move forgery (CMF). As both regions usually have same texture properties, therefore, this artifact is invisible for the viewers and credibility of the image becomes questionable in proof centered applications. Hence, means are required to validate the integrity of the image and identify the tampered regions. Image forensic techniques determine the integrity of the images by applying various high-tech mechanisms developed in the literature. In this dissertation, three techniques for copy-move forgery detection (CMFD) are presented to verify the truthfulness of image contents. Thus, for efficient detection of CMF, the first approach that we have presented exploits local binary pattern variance (LBPV) over the low approximation components of the stationary wavelets. The proposed CMFD method is applied over the circular regions to address the possible post-processing operations in a better way. The proposed method is evaluated on CoMoFoD (Copy Move Forgery Detection) and KLTCI (kodak lossless true color image) datasets in the presence of translation, flipping, blurring, rotation, scaling, color reduction, brightness change and multiple forged regions in an image. Our second method, presents an algorithm that utilizes stationary wavelet transform (SWT). The method exploits low approximation sub-band for forgery detection. The algorithm divides the low approximation sub-band into the small overlapping square blocks. A reduced feature vector representation is achieved by dividing each block into four triangles. The experimental results demonstrate that the algorithm is capable of detecting duplicated blocks precisely and identify multiple CMF effectively, even when the images are contaminated by blurring and noise. In our third method of CMFD, images are first divided into overlapping square blocks and DCT components are adopted as the block representations. Due to the high dimensional nature of the feature space, Gaussian radial basis function (RBF) kernel principal component analysis (PCA) is applied to achieve the reduced dimensional feature vector representation that also improved the efficiency during the feature matching step. Extensive experiments are performed on DVMM image forensic dataset and google images to evaluate the proposed method in comparison against state-of-the-arts. The experimental results reveal that the proposed technique precisely determines the CMF even when the images are contaminated with blurring, noise, compression and can effectively detect multiple CMF. All the three techniques presented in this dissertation are compared against renounced methods of CMFD over multiple image forensic datasets. The evaluation reveals the prominence of the presented methods as compared to state-of-the-arts. Consequently, the proposed techniques can reliably be applied to detect the forged regions and the benefits can be obtained in journalism, law enforcement, judiciary, and other proof critical domains.