Computationally synthesised inorganic and organometallic complexes : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Albany, New Zealand

Catalytic aromatic ring C–H bond functionalisations by transition metal cyclometallation reactions are important for organic transformation reactions. The cyclometallated product, which contains a new metal–carbon bond is formed as a consequence of different types of carbon–hydrogen····metal (C–H····M) interactions. These C–H···M interactions have been known as anagostic, preagostic and agostic interactions. By nature, the anagostic interaction has mainly electrostatic components, the preagostic interaction has electrostatic components with some back-bonding from metal to C–H antibonding orbital involved and the agostic interaction has mainly covalent components when the C–H bond donates electron density to the partially occupied metal centre. Prior to the current thesis work, an in-depth study that addresses the influence of steric and electronic factors on the anagostic, preagostic and agostic carbon–hydrogen····metal interaction was missing. In this thesis, the influence of both the steric and electronic factors on the anagostic, preagostic and agostic C–H···M interactions has been studied. It is seen that the electronic and steric influences play differently for different ligand systems as with the flexible tetralone ligand, a maximum of steric and electronic influence results into another type of anagostic interaction named as the 'C-anagostic' interaction. It is also seen that a stronger steric and electronic effect can trigger agostic covalency at the anagostic stage of the reaction. The inflexible ligand ensures the short anagostic approach, which has some back-bonding character and the nature of the interaction lies into the preagostic category. Finally, the aromatic ring agostic interactions have more complexity as new donations named as 'syndetic' from C–C pi bond to metal antibonding orbitals were recognised which shares the same antibonding acceptor orbitals as the agostic donation does. The recognition of new bonding situations in C–H····M interactions can have significant implications for C–H bond functionalisation reactions

A Vision of DevOps Requirements Change Management Standardization

DevOps (development and operations) aims to shorten the software development process and provide continuous delivery with high software quality. To get the potential gains of DevOps, the software development industry considering global software development (GSD) environment to hire skilled human resources and round-the-clock working hours. However, due to the lack of frequent communication and coordination in GSD, the planning and managing of the requirements change process becomes a challenging task. As in DevOps, requirements are not only shaped by development feedback but also by the operations team. This means requirements affect development, development affects operations and operations affect requirements. However, DevOps in GSD still faces many challenges in terms of requirement management. The purpose of this research project is to develop a DevOps requirement change management and implementation maturity model (DevOps-RCMIMM) that could assist the GSD organizations in modifying and improving their requirement management process in the DevOps process. The development of DevOps-RCMIMM will be based on the existing DevOps and RCM literature, industrial empirical study, and understanding of factors that could impact the implementation of the DevOps requirement change management process in the domain of GSD. This vision study presents the initial results of a systematic literature review that will contribute to the development of maturity levels of the proposed DevOps-RCMIMM

Quantum Software Engineering: A New Genre of Computing

Quantum computing (QC) is no longer only a scientific interest but is rapidly becoming an industrially available technology that can potentially tackle the limitations of classical computing. Over the last few years, major technology giants have invested in developing hardware and programming frameworks to develop quantum-specific applications. QC hardware technologies are gaining momentum, however, operationalizing the QC technologies trigger the need for software-intensive methodologies, techniques, processes, tools, roles, and responsibilities for developing industrial-centric quantum software applications. This paper presents the vision of the quantum software engineering (QSE) life cycle consisting of quantum requirements engineering, quantum software design, quantum software implementation, quantum software testing, and quantum software maintenance. This paper particularly calls for joint contributions of software engineering research and industrial community to present real-world solutions to support the entire quantum software development activities. The proposed vision facilitates the researchers and practitioners to propose new processes, reference architectures, novel tools, and practices to leverage quantum computers and develop emerging and next generations of quantum software

Dyslipidemia and mean lipid profile in patients with liver cirrhosis

Background: Patients with liver disorders are often found to have deranged lipid profile. Clear decline is observed in the levels of cholesterol as well as TG among individuals having severe hepatitis and liver failure as synthesis of lipoprotein is reduced. This study was done to determine the frequency of dyslipidemia and the mean lipid profile values in patients of liver cirrhosis.Methods: A cross sectional, descriptive study, done at the Department of Medicine, Medical Unit-1, Bahawal Victoria Hospital, Bahawalpur, from July to December 2019. A total of 246 patients presented with cirrhosis of liver of age 20-60 years and both genders were included. Analysis for serum total cholesterol (TC) level, serum triglycerides level, low density lipoprotein (LDL) and high density lipoprotein (HDL) were done and findings were noted.Results: Mean age was 51.67±6.21 years. Out of the 246 patients, 153 (62.20%) were male and 93 (37.80%) were females with male to female ratio of 1.6:1. Mean values of lipid were, LDL cholesterol 95.76±29.65 mg/dl, HDL 43.37±11.46 mg/dl, TC 147.51±42.69 mg/dl and TG 101.29±21.59 mg/dl. Dyslipidemia was found in 59 (23.98%) patients, whereas there was no dyslipidemia in 187 (76.02%) patients.Conclusions: Frequency of dyslipidemia in cirrhotic patients is high. Evaluating patients of liver cirrhosis, dyslipidemia need to be considered for early recognition and analysis

A Potential Approach to Enhance the Seebeck Coefficient of UHMWPE by Using the Graphene Oxide

Thermoelectric materials have been a competent source for the production of energy in the present decade. The most important and potential parameter required for the material to have better thermoelectric characteristics is the Seebeck coefficient. In this work, ultra high molecular weight polyethylene (UHMWPE) and graphene oxide (GO) nanocomposites were prepared by mechanical mixing by containing 10000ppm, 50000ppm, 70000ppm, 100000ppm, 150000ppm, and 200000ppm loadings of graphene oxide. Due to the intrinsic insulating nature of UHMWPE, the value of Seebeck for pristine UHMWPE and its nanocomposites with 10000ppm & 50000ppm of GO concentration was too low to be detected. However, the Seebeck coefficient for composites with 70000ppm, 100000ppm, 150000ppm, and 200000ppm loadings of GO was found to be 180, 206, 230, and 235 µV/ K, respectively. These higher values of Seebeck coefficients were attributed to the superior thermal insulating nature of UHMWPE and the conductive network induced by the GO within the UHMWPE insulating matrix. Although, the values of the figure of merit and power factor were negligibly small due to the lower concentration of charge carriers in UHMWPE/ GO nanocomposites but still reported, results are extremely hopeful for considering the composite as the potential candidate for thermoelectric applications

Empyema thoracis in children: clinical presentation, management and complications

Objective: To determine the etiology, clinical manifestation, management (medical and surgical) and complications of children with empyema thoracis in a tertiary care hospital from Karachi, Pakistan. Study Design: Descriptive, analytical study. Place and Duration of Study: Department of Surgery, The Aga Khan University Hospital, Karachi, from January 1996 to December 2010. Methodology: Medical records of admitted children aged \u3e a month to 15 years with discharge diagnosis of empyema thoracis and data was collected on demographic features, clinical manifestation, management and complications. Children managed medically were compared with those managed surgically by using interquartile range and median comparison. Mann-Whitney U test was used to compare age in months, weight (kg) and length of stay in days and presenting complaint, duration of illness; chi-square test was used to compare thrombocytosis in between groups and p-value was calculated. Results: Among the 112 patients, 59 (53%) were younger than 5 years of age. Males (n=83, 74%) were predominant. Fifty (45%) children were admitted in winter. Thirty (27%) children found unvaccinated and one fourth (n=27; 24%) were severely malnourished. Fever, cough, and dyspnea were the major presenting symptoms. Sixty-six (59%) were on some antibiotics prior to admission. Staphylococcus aureus (n=13) and Streptococcus pneumoniae (n=5) were the commonest organism isolated from blood and pleural fluid cultures. Majority of the children required some surgical intervention (n=86). Surgically managed children were younger (p=0.01); had less weight (p=0.01) and prolonged fever (p=0.02); and stayed longer in hospital (p \u3c 0.001) as compared to medically managed children. Requiring readmission (n=8), subcutaneous emphysema (n=5) and recollection of pus (n=5) were the major complications. Conclusion: Staphylococcus aureus was the major organism associated with paediatric empyema thoracis. Early identification and empiric antibiotic as per local data is essential to prevent short and long-term complications. Younger, lower weight children with prolonged fever required surgical management

N-(2-Meth­oxy­phen­yl)benzene­sulfonamide

The asymmetric unit of the title compound, C13H13NO3S, contains two crystallographically independent mol­ecules in which the dihedral angles between the phenyl and benzene rings are 88.16 (12) and 44.50 (12)°. One of the mol­ecules features an intra­molecular N—H⋯O hydrogen bond. In the crystal, the mol­ecules are linked into dimers by pairs of N—H⋯O hydrogen bonds. The dimers are further connected by C—H⋯O and C—H⋯π inter­actions, forming a three-dimensional network

EVALUATION OF PLANTING METHODS FOR GRAIN YIELD AND YIELD COMPONENTS OF WHEAT

ABSTRACT The present experiment was conducted at Agricultural Research Farm, NWFP agricultural University Peshawar during 2004-05, to evaluate the effect of different planting methods on yield components of wheat, using randomized complete block design with four replications. Planting methods evaluated were: Line planting (20cm apart), Line planting (30cm apart), Cross planting, Broadcast planting, Single row on ridge, and Double row on single ridge. Line planted wheat 30cm apart produced significantly higher number of spikes m -2 (164), thousand grain weight (39.85g) and grain yield (5164 kg ha (57), thousand grain weight (32.09 g) and grain yield (4088 kg ha -1 ). This study shows that line planting 30cm apart gives better results for grain yield of wheat than broadcast and other planting methods studied