520 research outputs found

    A NEW CLASS OF LUMINESCENT ORGANOMETALLICS -DIETHYNYLRHODACYCLOPENTADIENES

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    The main objective in this project is to develop a greater understanding of the unusual photophysical properties of 2,5-bis(arylethynyl)rhodacyclopentadienes. Three distinct and unusual photophysical properties were found in the 2,5-bis(arylethynyl)-rhodacyclopentadienes: (i) long-lived singlet excited states, from which some of them exhibit high-intensity fluorescence with nanosecond lifetimes; (ii) slow intersystem crossing rates (k values ≈ 108 s-1) compared to typical luminescent organometallic complexes (with k values ≈ 1012 s-1); and (iii) no phosphorescence was observed even at 77 K in a rigid glass. Many photophysical experiments such as e.g. low-temperature lifetime measurments, singlet oxygen sensitisation and time-resolved infrared (TRIR) have been carried out in order to investigate further and explain the unusual photophysical properties of this class of organometallic complexes. Five different types of ligand X on 2,5-bis(p-R-arylethynyl)-X-rhodacyclopentadienes [X = 4-[4-(N,N-di-n-hexylamino)phenylethynyl]phenylethynyl- (DHAPEPE-), trimethyl silylethynyl- (TMSE-), methyl- (Me-), η2-benzoato- and acetylacetonato- (acac-)] have been synthesised and the photophysical properties of the complexes were investigated. The TMSE-rhodacyclopentadienes gave the highest fluorescence quantum yields compared to the other series of rhodacyclopentadienes. Extended phenylene-ethynylene ligands (i.e. DHAPEPE-) did not impart any effects on the max values in absorption and emission but the quantum yields were lower than those for the TMSE-rhodacyclopentadienes. η2-Benzoato- and acac- ligands shifted the max values in absorption and emission to lower energy, which implies that they induce smaller energy gaps between the excited and ground states. The emissions from the η2-benzoato-rhodacyclopentadienes were quenched (especially for those with R = H and SMe substituents, which have quantum yields of less than 0.01). The first example of isomeric biphenyl-rhodacyclopentadiene by-product formation was found in the synthesis of acac-rhodacyclopentadienes. The isomeric biphenyl-rhodacyclopentadiene by-product with R = CO2Me was isolated and its molecular structure was confirmed by X-ray analysis. Its emission spectrum shows two emission bands with max values of 394 and 544 nm in degassed toluene solution. The fluorescent emission at 394 nm has a quantum yield of 0.03, whereas the phosphorescent emission at 544 nm has a quantum yield of 0.05. The unusual long lifetime (237.6 s) of the phosphorescence at room temperature indicates that the transition is from a ligand-centred (LC) * transition. In addition, the syntheses of 1,4-bis(p-R-phenyl)buta-1,3-diynes and novel 1,12-bis(p-R-phenyl)dodaca-1,3,9,11-tetraynes, which serve as the starting materials for the synthesis of the rhodacyclopentadienes, are also reported. Four novel 1,12-bis(p-R-phenyl)dodaca-1,3,9,11-tetraynes (where R = H, SMe, CO2Me and BMes2) have been synthesised and characterised. The formation of homo-coupling products was a major problem which reduced the yields of the 1,3,9,11-dodacatetraynes. The 1,3,9,11-dodacatetraynes were separated from their respective homo-coupling products using column chromatography, and the yields obtained were 30 – 46%

    A Complete Characterisation of Vertex-multiplications of Trees with Diameter 5

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    For a connected graph GG, let D(G)\mathscr{D}(G) be the family of strong orientations of GG; and for any DD(G)D\in\mathscr{D}(G), we denote by d(D)d(D) the diameter of DD. The orientation number\textit{orientation number} of GG is defined as dˉ(G)=min{d(D)DD(G)}\bar{d}(G)=\min\{d(D)\mid D\in \mathscr{D}(G)\}. In 2000, Koh and Tay introduced a new family of graphs, GG vertex-multiplications, and extended the results on the orientation number of complete nn-partite graphs. Suppose GG has the vertex set V(G)={v1,v2,,vn}V(G)=\{v_1,v_2,\ldots, v_n\}. For any sequence of nn positive integers (si)(s_i), a GG \textit{vertex-multiplication}, denoted by G(s1,s2,,sn)G(s_1, s_2,\ldots, s_n), is the graph with vertex set V=i=1nViV^*=\bigcup_{i=1}^n{V_i} and edge set EE^*, where ViV_i\u27s are pairwise disjoint sets with Vi=si|V_i|=s_i, for i=1,2,,ni=1,2,\ldots,n; and for any u,vVu,v\in V^*, uvEuv\in E^* if and only if uViu\in V_i and vVjv\in V_j for some i,j{1,2,,n}i,j\in \{1,2,\ldots, n\} with iji\neq j such that vivjE(G)v_i v_j\in E(G). They proved a fundamental classification of GG vertex-multiplications, with si2s_i\ge 2 for all i=1,2,,ni=1,2,\ldots, n, into three classes C0,C1\mathscr{C}_0, \mathscr{C}_1 and C2\mathscr{C}_2, and any vertex-multiplication of a tree with diameter at least 3 does not belong to the class C2\mathscr{C}_2. Furthermore, some necessary and sufficient conditions for C0\mathscr{C}_0 were established for vertex-multiplications of trees with diameter 55. In this paper, we give a complete characterisation of vertex-multiplications of trees with diameter 55 in C0\mathscr{C}_0 and C1\mathscr{C}_1

    Optimal orientations of Vertex-multiplications of Trees with Diameter 4

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    \noindent Koh and Tay proved a fundamental classification of GG vertex-multiplications into three classes C0,C1\mathscr{C}_0, \mathscr{C}_1 and C2\mathscr{C}_2. They also showed that any vertex-multiplication of a tree with diameter at least 3 does not belong to the class C2\mathscr{C}_2. Of interest, GG vertex-multiplications are extensions of complete nn-partite graphs and Gutin characterised complete bipartite graphs with orientation number 3 (or 4 resp.) via an ingenious use of Sperner\u27s theorem. In this paper, we investigate vertex-multiplications of trees with diameter 44 in C0\mathscr{C}_0 (or C1\mathscr{C}_1) and exhibit its intricate connections with problems in Sperner Theory, thereby extending Gutin\u27s approach. Let ss denote the vertex-multiplication of the central vertex. We almost completely characterise the case of even ss and give a complete characterisation for the case of odd s3s\ge 3

    Synthesis of New Star-Shaped Liquid Crystalline Cyclotriphosphazene Derivatives with Fire Retardancy Bearing Amide-Azo and Azo-Azo Linking Units

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    Two series of new hexasubstituted cyclotriphosphazene derivatives were successfully synthesized and characterized. These derivatives are differentiated by two types of linking units in the molecules such as amide-azo (6a–j) and azo-azo (8a–j). The homologues of the same series contain different terminal substituents such as heptyl, nonyl, decyl, dodecyl, tetradecyl, hydroxyl, carboxyl, chloro, nitro, and amino groups. All the intermediates and final compounds were characterized using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), and Carbon, Hydrogen, and Nitrogen (CHN) elemental analysis. Liquid crystal properties for all compounds were determined using polarized optical microscope (POM). It was found that only intermediates 2a–e with nitro and alkoxyl terminal chains showed a smectic A phase. All the final compounds with alkoxyl substituents are mesogenic with either smectic A or C phases. However, other intermediates and compounds were found to be non-mesogenic. The study on the fire retardancy of final compounds was determined using limiting oxygen index (LOI) method. The LOI value of pure polyester resin (22.53%) was increased up to 24.71% after treating with 1 wt% of hexachlorocyclotriphosphazene (HCCP). Moreover, all the compounds gave positive results on the LOI values and compound 6i with the nitro terminal substituent showed the highest LOI value of 27.54%

    Dynamics and characterisation of membrane fouling in a long reverse osmosis membrane channel

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    Ph.DDOCTOR OF PHILOSOPH

    Species diversity of under-storey birds at mount Jagoi, Bau, Sarawak

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    Avifauna surveys were conducted at four sites in Mount Jagoi, Bau in August and November 2011, and February 2012. The main objective of the survey was to catalogue a checklist of under-storey birds. This study also compared the species diversity of avifauna at different locations in that area. Twenty mist-nets were deployed for five days in each site, from 0600 to 1800 hour daily. A total of 296 birds from 52 species representing 21 families were captured. Little Spiderhunter (Arachnothera longirostra) was the most abundant species mist-netted (27.4%) and family Pycnonotidae had the most diverse species caught. Statistical analysis showed that there is significant difference between all the study sites

    Membrane-less microfiltration using inertial microfluidics

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    Microfiltration is a ubiquitous and often crucial part of many industrial processes, including biopharmaceutical manufacturing. Yet, all existing filtration systems suffer from the issue of membrane clogging, which fundamentally limits the efficiency and reliability of the filtration process. Herein, we report the development of a membrane-less microfiltration system by massively parallelizing inertial microfluidics to achieve a macroscopic volume processing rates (~ 500 mL/min). We demonstrated the systems engineered for CHO (10–20 μm) and yeast (3–5 μm) cells filtration, which are two main cell types used for large-scale bioreactors. Our proposed system can replace existing filtration membrane and provide passive (no external force fields), continuous filtration, thus eliminating the need for membrane replacement. This platform has the desirable combinations of high throughput, low-cost, and scalability, making it compatible for a myriad of microfiltration applications and industrial purposes.Singapore. National Research Foundation (Singapore-MIT Alliance for Research and Technology)United States. Advanced Research Projects Agency-Energy (Grant DE-AR0000294

    Microvascular and macrovascular complications of type 2 diabetes mellitus: Exome wide association analyses

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    Background: Type 2 diabetes mellitus (T2DM) is a chronic, metabolic disorder in which concomitant insulin resistance and β-cell impairment lead to hyperglycemia, influenced by genetic and environmental factors. T2DM is associated with long-term complications that have contributed to the burden of morbidity and mortality worldwide. The objective of this manuscript is to conduct an Exome-Wide Association Study (EWAS) on T2DM Emirati individuals to improve our understanding on diabetes-related complications to improve early diagnostic methods and treatment strategies. Methods: This cross-sectional study recruited 310 Emirati participants that were stratified according to their medically diagnosed diabetes-related complications: diabetic retinopathy, diabetic neuropathy, diabetic nephropathy, and cardiovascular complications. The Illumina’s Infinium Exome-24 array was used and 39,840 SNPs remained for analysis after quality control. Findings: The analysis revealed the associations of various genes with each complication category: 1) diabetic retinopathy was associated to SHANK3 gene in locus 22q13.33 (SNP rs9616915; p=5.18 x10-4), ZSCAN5A gene in locus 19q13.43 (SNP rs7252603; p=7.55 x10-4), and DCP1B gene in locus 12p13.33 (SNPs rs715146, rs1044950, rs113147414, rs34730825; p=7.62 x10-4); 2) diabetic neuropathy was associated to ADH4 gene in locus 4q23 (SNP rs4148883; p=1.23 x10-4), SLC11A1 gene in locus 2q35 (SNP rs17235409; p=1.85 x10-4), and MATN4 gene in locus 20q13.12 (SNP rs2072788; p=2.68 x10-4); 3) diabetic nephropathy was associated to PPP1R3A gene in locus 7q31.1 (SNP rs1799999; p=1.91 x10-4), ZNF136 gene in locus 19p13.2 (SNP rs140861589; p=2.80 x10-4), and HSPA12B gene in locus 20p13 (SNP rs6076550; p=2.86 x10-4); and 4) cardiovascular complications was associated to PCNT gene in locus 21q22.3 (SNPs rs7279204, rs6518289, rs2839227, rs2839223; p=2.18 x10-4,3.04 x10-4,4.51 x10-4,5.22 x10-4 respectively), SEPT14 gene in locus 7p11.2 (SNP rs146350220; p=2.77 x10-4), and WDR73 gene in locus 15q25.2 (SNP rs72750868; p=4.47 x10-4). Interpretation: We have identified susceptibility loci associated with each category of T2DM-related complications in the Emirati population. Given that only 16% of the markers from the Illumina’s Infinium Exome chip passed quality control assessment, this demonstrates that multiple variants were, either, monomorphic in the Arab population or were not genotyped due to the use of a Euro-centric EWAS array that limits the possibility of including targeted ethnic-specific SNPs. Our results suggest the alarming possibility that lack of representation in reference panels could inhibit discovery of functionally important loci associated to T2DM complications. Further effort must be conducted to improve the representation of diverse populations in genotyping and sequencing studies
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