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

The Urban Informal Sector in an Adjusting Economy: The Case of Pakistan

The concept of the informal sector has gained popularity since the well-known study by International Labour Organisation [ILO] in 1972 Kenya. Since then it has become a centre stage in policy discussion regarding unemployment and poverty alleviation. Though economists are still not able to give an authentic and unanimous definition of the informal sector, it is commonly known as the non-regulated sector of the economy. Despite the fact that the informal sector provides a large chunk of GDP and employment in the national economy, this sector is very much neglected in Pakistan. A few studies have been conducted to measure the size and the role of urban informal sector in past. However, the employment estimates provided by these studies have always been controversial. In addition, in all of these studies attention has been focused mainly to the manufacturing sector. Though the importance of the manufacturing sector cannot be denied, the services sector is also of significant importance as well, however it has received relatively less attention in the past. In this study, sufficient attention has been given to this neglected sector and focus is given to its role in employment in the urban informal sector.

A Low Temperature And Pressure Methanol Synthesis

Researchers and industrial practitioners have been discussed a lot about methanol synthesis nowadays. This is because due to the high demand of methanol itself in processing formaldehyde, chloromethanes, amines, acetic acid, MTBE and methyl methacrylate. In addition of that, currently methanol synthesis using syngas has attracted this researchers and industrial practitioner since it involving greenhouse gas which is CO2. Methanol synthesis reaction is an exothermic reaction. Researchers are still trying to find a way to lower down the operating conditions (e. g temperature and pressure) because of controlling the temperature inside the reactor is difficult. Besides, high operating conditions may deactivate the catalyst, thus lowering down the CO conversion, yield and not less may lowering down the selectivity of methanol. Since that sulphur free synthesis gas has been able to produce, Cu-based catalyst, a more active catalyst can be used and a low pressure and temperature methanol synthesis is more feasible. The study on low temperature methanol synthesis using 2-butanol has been successful and currently been applied in big scale. However, there is still no well-establish study on low temperature and pressure using aromatics solvent as catalytic solvent, thus gain the author interest to study on this matter. In the first semester, the author come out with some theory about how methanol is produced after done some deep research. The project continued in the second semester with catalyst preparing, catalyst characterization, run methanol synthesis reaction in a three phase reactor and samples analysis. In this project, two aromatics solvents (toluene and xylene) is use in the process of synthesizing methanol at temperature of 150 - 200°C and pressure of 20 bar. Percentage of total carbon conversion and yield will be observed as well as the selectivity at the end of this projec

Wheat growth and phytoavailability of copper and zinc as affected by soil texture in saline-sodic conditions

Nutrient disorders in saline-sodic soils can adversely affect crop growth. In order to evaluate the growth response of wheat (Triticum aestivum L.) to Cu and Zn and the phytoavailability of these essential elements, a pot experiment was conducted in three different textured saline-sodic soils [sandy loam (SL), sandy clay loam (SCL) and clay (C)] having an ECe 8.63, 8.80, 8.98 dS m–1 and SAR 21.66, 23.48, 24.84 (mmol L–1)1/2 respectively. Seven treatments including levels of Cu (4, 6 and 8 mg kg–1) and levels of Zn (4, 6 and 8 mg kg–1) were separately applied together with a single control treatment. Dry matter yield (straw + grain) of wheat increased up to 35.2% with Cu and up to 31.2 % with Zn application relative to the control. As soil clay content increased, dry matter yield decreased up to 39.2% in SCL and up to 62.7% in C soil when compared to SL soil. Application of Cu increased the concentration in both wheat straw and grains up to 2.46 and 2.20 mg kg–1 DW respectively relative to the control. Zinc concentration in wheat straw and grains was also increased up to 29.97 and 29.40 mg kg–1 DW respectively relative to the controls. Copper application significantly increased Zn concentrations in wheat plants

Konstruksi Konsep Dakwah dan Syarah Hadis Oral Habib Ja’far bin Husein dalam Akun YouTube Jeda Nulis

Habib Ja'far's Hadith in the Jeda Nulis account. Starting from the initial assumption that, the purpose of creating the 'Jeda Nulis' account is to convey Habib Ja'far's ideas and thoughts visually based on the tendency of the millennial generation who prefer da'wah material in the form of comedy. Therefore, there are at least three questions raised This paper intends to examine the construction of the concept of da'wah and oral sharia in this article. 1)How is the construction of Habib Ja'far's da'wah concept based on the Hadith of the Prophet. 2)How are the religious tendencies and discourses in Habib Ja'far's oral Hadith sketches. 3)What are the implications for the concept of da'wah and diversity in the modern era. This type of research is literature using descriptive-qualitative methods with a critical paradigm. This research concludes that, one form of construction of Habib Ja'far's da'wah concept is to change the face of da'wah which tends to be rigid with comedic da'wah nuances based on the Prophet's hadith Ithaf al-shuruf fiqalb ikhwa. According to him, it is necessary to distinguish between propagating religion and diversifying jokes, what he does is use a touch of comedy with the aim of diversifying jokes. The implications of this da'wah concept lead to two aspects, namely positive and negative implications.Hadis Habib Ja’far dalam akun Jeda Nulis. Berangkat dari asumsi awal bahwa, tujuan dibuatnya akun ‘Jeda Nulis’ ialah untuk menyampaikan gagasan-gagasan serta pemikiran Habib Ja’far secara visual berdasarkan kecenderungan para generasi milineal yang lebih menyukai materi dakwah dalam bentuk komedi. Olehnya, setidaknya terdapat tiga pertanyaan yang diajukan Tulisan ini bermaksud untuk mengkaji tentang konstruksi konsep dakwah dan syarah oral dalam artikel ini. 1)Bagaimana bentuk konstruksi konsep dakwah Habib Ja’far yang didasarkan pada Hadis Nabi Saw. 2)Bagaimana kecenderungan dan wacana keagamaan dalam syarah Hadis oral Habib Ja’far. 3)Bagaimana implikasinya terhadap konsep dakwah dan keberagamaan era modern. Jenis penelitian ini ialah kepustakaan menggunakan metode deskriptif-kualitatif dengan paradigma kritis. Peneltian ini menyimpulkan bahwa, salah satu bentuk konstruksi konsep dakwah Habib Ja’far ialah dengan mengubah wajah dakwah yang cenderung kaku dengan nuansa dakwah komedi yang berdasar pada hadis Nabi saw Ithaf al-shuruf fiqalb ikhwa. Menurutnya, perlu untuk dibedakan antara membercandakan agama dengan mengagamakan canda, yang dilakukan olehnya ialah menggunakan sentuhan komedi dengan tujuan mengagamakan canda. Adapun implikasi dari konsep dakwah ini mengarah pada dua aspek yakni berimplikasi positif dan negatif

Role of RNA Interference (RNAi) in the Moss Physcomitrella patens

RNA interference (RNAi) is a mechanism that regulates genes by either transcriptional (TGS) or posttranscriptional gene silencing (PTGS), required for genome maintenance and proper development of an organism. Small non-coding RNAs are the key players in RNAi and have been intensively studied in eukaryotes. In plants, several classes of small RNAs with specific sizes and dedicated functions have evolved. The major classes of small RNAs include microRNAs (miRNAs) and small interfering RNAs (siRNAs), which differ in their biogenesis. miRNAs are synthesized from a short hairpin structure while siRNAs are derived from long double-stranded RNAs (dsRNA). Both miRNA and siRNAs control the expression of cognate target RNAs by binding to reverse complementary sequences mediating cleavage or translational inhibition of the target RNA. They also act on the DNA and cause epigenetic changes such as DNA methylation and histone modifications. In the last years, the analysis of plant RNAi pathways was extended to the bryophyte Physcomitrella patens, a non-flowering, non-vascular ancient land plant that diverged from the lineage of seed plants approximately 450 million years ago. Based on a number of characteristic features and its phylogenetic key position in land plant evolution P. patens emerged as a plant model species to address basic as well as applied topics in plant biology. Here we summarize the current knowledge on the role of RNAi in P. patens that shows functional overlap with RNAi pathways from seed plants, and also unique features specific to this species

Penerapan model pembelajaran problem based instruction untuk meningkatkan hasil belajar siswa kelas X MAN Semarang 1 pada mata pelajaran fisika materi pokok hukum Newton tentang gerak tahun ajaran 2009/2010

Pembelajaran fisika pada umumnya masih didominasi guru yang menggunakan metode ceramah dan kurang melibatkan aktivitas siswa dalam melakukan kerja ilmiah, akibatnya hasil belajar siswa masih rendah dan kegiatan belajar siswa pun belum menyentuh aspek afektif dan aspek psikomotorik. Guru perlu mencari inovasi strategi belajar mengajar yang melibatkan siswa dalam pembelajaran untuk mencapai hasil belajar yang baik dan dapat mengembangkan keaktifan siswa. Penelitian ini bertujuan untuk meningkatkan hasil belajar siswa kelas X-2 MAN Semarang 1 pada mata pelajaran fisika materi pokok hukum Newton tentang gerak melalui penerapan model pembelajaran Problem Based Instruction. Penelitian ini merupakan penelitian tindakan kelas yang dilaksanakan dalam tiga siklus. Tiap siklusnya meliputi 4 tahap yakni, perencanaan, pelaksanaan, pengamatan dan refleksi. Faktor yang diteliti adalah hasil belajar siswa (kognitif, afektif, psikomotorik). Data hasil belajar kognitif diambil dari nilai tes setiap akhir siklus. Data hasil belajar afektif dan psikomotorik diperoleh dari lembar observasi. Dari hasil penelitian, hasil belajar kognitif siswa sebelum tindakan masih dibawah rata-rata yaitu 55,75 dengan presentase ketuntasan 33,33%. Pada siklus I, nilai tes rerata 64,11 dengan presentase ketuntasan 52,77%. Pada siklus II, nilai tes rerata 72,56 dengan presentase ketuntasan 75%. Pada siklus III, nilai tes rerata 75,94 dengan presentase ketuntasan 88,88%. Hasil belajar afektif pada siklus I, diketahui nilai presentase ketuntasannya 53,75%. Pada siklus II, nilai presentase ketuntasannya 64,44%. Pada siklus III, nilai presentase ketuntasannya 75,50%. Hasil belajar psikomotorik pada siklus I, diketahui nilai presentase ketuntasannya 52,22%. Pada siklus II, nilai presentase ketuntasannya 58,89%. Pada siklus III, nilai presentase ketuntasannya 70,14%, sehingga dapat disimpulkan bahwa dengan penerapan Problem Based Instruction pada materi pokok Hukum Newton tentang gerak dapat meningkatkan hasil belajar siswa kelas X MAN Semarang I tahun ajaran 2009/2010. Peningkatan hasil belajar dapat dilihat dari kenaikan nilai rerata dan ketuntasan belajar dari satu siklus ke siklus berikutnya. Diharapkan dengan penerapan Problem Based Instruction dalam pembelajaran físika dapat membantu siswa mengembangkan kemampuan berpikir dan memecahkan masalah melalui pelibatan dengan pengalaman nyata sehingga hasil belajar siswa bisa lebih optimal. Kata kunci: Problem Based Instruction, Hasil Belaja

Calcium Homeostasis in Escherichia coli: Characterization of Mutants and Genome Expression of MG1655

While the role of calcium ions as secondary messengers has been well described in eukaryotic cells, little is known about calcium homeostasis in bacteria at the physiological and molecular levels. Genetic and genomic approaches were used to address calcium regulation and to identify genes (cal) involved in calcium homeostasis. Transposon mutagenesis of Escherichia coli generated several calcium-sensitive mutants that fell into three categories: (i) Ca2+-sensitive chemotaxis mutants, (ii) Ca2+-sensitive cell division mutants, and (iii) Ca2+-sensitive mutants that showed no defects in cell division or chemotaxis. The physiological properties of these Ca2+-sensitive mutants were determined. Besides calcium-sensitivity to 75 mM calcium, all of the mutants exhibited increased sensitivities to several divalent cations including Ni2+, Mg2+, Mn2+, Co2+, Zn2+, Cu2+, and Cd2+. To identify the cal gene sequence in the Ca2+-sensitive mutants, the region of the genes fused to the reporter gene (phoA) on the transposon TnphoA was amplified by PCR and sequenced. The sites of the gene fusion for three cal mutants were at the fdoG, gpt and pqi5 genes. The pleiotropic nature for the cal mutations suggested that many genes may be globally regulated by calcium. We then investigated global gene expression patterns of wild-type E. coli under calcium-depleted (addition of 10 mM EGTA) and calcium-elevated (addition of 75 mM Ca2+) conditions as compared to cultures grown under unstressed conditions. A comprehensive transcriptome analysis using macroarrys exhibited a global regulation of diverse genes within the E. coli genome during calcium homeostasis

PENGARUH QUALITY PRACTICES TERHADAP CUSTOMER SATISFACTION DAN BUSINESS RESULT PADA USAHA PERABOT DI KOTA BANDA ACEH

ABSTRAKPenelitian ini bertujuan untuk mengetahui pengaruh quality practice terhadap customer satisfaction dan business result Usaha Perabot di Kota Banda Aceh. Dalam penelitian ini, customer satisfaction dijadikan intervening variable antara quality practice dan business result. Sampel penelitian sebanyak 50 orang pengelola Usaha Perabot, dan selanjutnya data dianalisis dengan menggunakan peralatan statistik regresi bertingkat. Penelitian menemukan bahwa quality practice berpengaruh positifi dan signifikan terhadap customer satisfaction dan business result. Keberadaan customer satisfaction dapat menjadi variabel perantara antara business result dan quality practice. Efek mediasi yang dimunculkan oleh customer satisfaction adalah mediasi parsial.Kata Kunci:Business Result, Customer Satisfaction, Quality Practice and Hierarchical Linier Methods, Usaha Perabo