Дисертації з теми "Group 13"
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1
Bullock, Thomas Hornsby. "Group 13 tris-pyridyl complexes." Thesis, University of Cambridge, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.578971.
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Silverman, Joel Samuel. "Adventures in group 13 chemistry /." Digital version accessible at:, 1999. http://wwwlib.umi.com/cr/utexas/main.
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Mitra, Amitabha. "GROUP 13 CHELATES IN PHOSPHATE DEALKYLATION." UKnowledge, 2006. http://uknowledge.uky.edu/gradschool_diss/293.
Повний текст джерелаАнотація:
A series of mononuclear boron halides of the type LBX2 (LH = N-phenyl-3,5-di-tbutylsalicylaldimine,X = Cl (2), Br (3)) and LBX ( LH2 = N-(2-hydroxyphenyl)-3,5-di-tbutylsalicylaldimine,X = Cl (7), Br (8); LH2 = N-(2-hydroxyethyl)-3,5-di-tbutylsalicylaldimine,X = Cl (9), Br (10); LH2= N-(3-hydroxypropyl)-3,5-di-tbutylsalicylaldimine,X = Cl (11), Br (12)) were synthesized from their borate precursorsLB(OMe)2 (1) (LH = N-phenyl-3,5-di-t-butylsalicylaldimine ) and LB(OMe) (LH2 = N-(2-hydroxyphenyl)-3,5-di-t-butylsalicylaldimine (4), N-(2-hydroxyethyl)-3,5-di-tbutylsalicylaldimine(5), N-(3-hydroxypropyl)-3,5-di-t-butylsalicylaldimine (6)). Theborate precursors, 1, 4 - 6, in turn, were prepared by refluxing the corresponding ligandsLH or LH2 with excess B(OMe)3. The boron halide compounds were air- and moisturesensitiveand compound 7 on hydrolysis gave the oxo-bridged compound 13 thatcontained two seven-membered boron heterocycles. The boron halide compoundsdealkylated trimethyl phosphate in stoichiometric reactions to produce methyl halide andunidentified phosphate materials. Compounds 8 and 12 were found to be the mosteffective dealkylating agents. Compound 8 on reaction with t-butyl diphenyl phosphinateproduced a unique boron phosphinate compound LB(O)OPPh2 (14) containing a terminalphosphinate group. Compounds 1-14 were characterized by 1H, 13C, 11B, 31P NMR, IR,MS, EA and MP. Compounds 5, 6, 11, 12 and 13 were also characterized by singlecrystalX-ray diffraction.The alkane elimination reaction between Salen(tBu)H2 ligands and diethylaluminumbromide was used to prepare the four Salen aluminum bromide compounds,salen(tBu)AlBr (15) (salen = N,N'-ethylenebis(3,5-di-tert-butylsalicylideneimine)),salpen(tBu)AlBr (16) (salpen = N,N'-propylenebis(3,5-di-tert-butylsalicylideneimine)),salben(tBu)AlBr (17) (salben = N,N'-butylenebis(3,5-di-tert-butylsalicylideneimine)) andsalophen(tBu)AlBr (18) (salophen = N,N'-o-phenylenenebis(3,5-di-tertbutylsalicylideneimine)).The compounds contained five-coordinate aluminum either in adistorted square planar or a trigonal bipyramidal environment. The bromide group inthese compounds could be displaced by triphenylphosphine oxide or triphenyl phosphateto produce the six-coordinate cationic aluminum compounds [salen(tBu)Al(Ph3PO)2]Br(19), [salpen(tBu)Al(Ph3PO)2]Br (20), [salophen(tBu)Al(Ph3PO)2]Br (21) and[salophen(tBu)Al{(PhO)3PO}2]Br (22). All the compounds were characterized by 1H,13C, 27Al and 31P NMR, IR, mass spectrometry and melting point. Furthermore,compounds 15, 16, 17, 18, 20, 21 and 22 were structurally characterized by single-crystalX-ray diffraction. Compounds 15, 17 and 18 dealkylated a series of organophosphates instoichiometric reaction by breaking the ester C–O bond. Also, they promoted thedealkylation reaction between trimethyl phosphate and added boron tribromide.Stoichiometric reaction of compound 15 with trimethyl phosphate produced thealuminophosphinate compound salen(tBu)AlOP(O)Ph2 (23). Compound 16 on reactionwith tributyl phosphate produced the aluminophosphate compound[salpen(tBu)AlO]2[(BuO)2PO]2 (24). Compounds 23 and 24 were characterized by singlecrystalX-ray diffraction and spectroscopically.
4
Tombul, Mustafa. "Towards heterometallic group 13 imido complexes." Thesis, University of Cambridge, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.620961.
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5
Ahmed, Shabana Almas. "Bis(phosphinimino) derivatives for Group 2 and Group 13 metals." Thesis, Imperial College London, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.434915.
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6
Bakewell, Clare Michelle. "Group 3 and Group 13 initiators for rac-lactide ring-opening polymerization." Thesis, Imperial College London, 2013. http://hdl.handle.net/10044/1/27290.
Повний текст джерелаАнотація:
This thesis describes the synthesis of a series of bis(quinolinolato)aluminium ethyl, (quinolinolato) gallium and (quinolinolato)zinc ethyl compounds which have been synthesised and fully characterised using spectroscopic techniques, elemental analyses and in some cases single crystal X-ray diffraction. The compounds are shown to be active initiators for the ring-opening polymerization of rac-lactide, with the activity being dependent on the metal, zinc > gallium > aluminium. All initiators show characteristics consistent with a controlled polymerization: predictable molecular weights and narrow polydispersities. The bis(quinolinolato)aluminium ethyl initiators all promote iso-selective ring-opening, with iso-selectivity values between 0.57 and 0.76. The degree of iso-selectivity is attributed to the steric hindrance imposed by the substituents on the ligands. The related gallium compounds show increased activity, whilst maintaining the good degree of stereocontrol. A series of yttrium phosphasalen compounds are also described and their activity for the ring-opening polymerization of rac-lactide is reported. The series of compounds vary at the diimine linker, the phenoxide substituents and at the alkoxide group. The compounds all show the rapid and controlled initiation of the ring-opening polymerization of lactide. The activity of the initiators was found to be dependent on the diimine linker: ethylene > cyclohexene > phenylene > propylene, and on the electron donating ability of the phenoxide substituent. All the initiators exerted a good degree of stereocontrol on the polymerization. Interestingly, the tacticity of the polymer was seen to switch from heterotactic polylactide (Ps 0.87) to isotactic polylactide (Pi 0.86), with the inclusion of an additional bonding nitrogen moiety in the diimine linker. The formation of isotactic polylactide using Group 3 initiators is extremely rare.
7
Ong, Christopher M. "Group 13 and 14 imine and phosphinimide complexes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/NQ62262.pdf.
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8
Scouter, Philip F. "Molecular compounds of the heavier Group 13 elements." Thesis, University of Oxford, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.308610.
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9
Tun, Zin-MIn. "Interactions of Group 13 Lewis Acids with Hexachlorocyclotriphosphazene." University of Akron / OhioLINK, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=akron1226945430.
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10
Bauer, Tobias [Verfasser], and Rhett [Akademischer Betreuer] Kempe. "Group 3 and Group 13 Metal Hydride Compounds / Tobias Bauer. Betreuer: Rhett Kempe." Bayreuth : Universität Bayreuth, 2013. http://d-nb.info/105935263X/34.
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11
Cannadine, Jason Christopher. "Development of group 13 organometallic complexes for acrylate polymerisation." Thesis, University of Warwick, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.282444.
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12
Harvey, Howard Glen. "The chemistry of new group 13 metal diphosphonate materials." Thesis, University College London (University of London), 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.407958.
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13
Riddlestone, Ian Martin. "Synthesis and reactivity of transition metal-group 13 complexes." Thesis, University of Oxford, 2013. http://ora.ox.ac.uk/objects/uuid:f253a2a5-cc6e-4978-86d9-5f3064dadc1b.
Повний текст джерелаАнотація:
The synthesis and reactivity of a number of mixed transition metal-aluminium and σ-alane complexes are detailed in this thesis. Chapter III reports on the formation and structural characterisation of N,N'-chelated aluminium dihalide precursors featuring amidinate and guanidinate substituents. These precursors of the type RC(R'N)2AlX2 (R = iPr2N or Ph; R' = Cy or iPr or Dipp; X = hal), readily react with Na[CpFe(CO)2] via salt elimination to form the corresponding mixed iron-aluminium complexes CpFe(CO)2[(X)Al(NR')2CR] which have been characterised both spectroscopically and by X-ray diffraction. The reactivity of the novel mixed aluminium-iron complexes towards halide abstraction agents has been investigated and a propensity for augmented coordination at the aluminium centre observed. Furthermore, complementary syntheses of the methyl substituted complex CpFe(CO)2[(Me)Al(NCy)2CNiPr2] have been developed. This can be achieved either via the reaction between the related chloride complex and MeLi, or from the reaction between iPr2C(CyN)2Al(Me)Cl and Na[CpFe(CO)2]. The research detailed in Chapter IV builds on the previous chapter and is focussed on the use of more sterically demanding substituents at both aluminium and transition metal, as well as more electron rich transition metal fragments. The transition metal anions Na[Cp*Fe(CO)2] and Na[CpSiFe(CO)(PPh3)] react with the aluminium precursors forming related mixed iron-aluminium complexes which have been structurally characterised. The Dipp2NacNacAlCl2 precursor has been shown to undergo reaction with both Na[CpFe(CO)2] and Na[Cp*Fe(CO)2]. The halide abstraction chemistry of the latter utilising both Lewis acid and salt metathesis based abstraction approaches has been investigated. The dehydrohalogenation chemistry of the Dipp2NacNacAlCl2 precursor was investigated and the ligand activated products of reactions with both alkyl lithium and alkyl potassium reagents characterised. Chapter V reports the extension of salt metathesis for the formation of an Al-H-Mn interaction, and the product has been fully characterised. In addition, the coordination of Al-H bonds from a number of alane precursors to in situ generated 16-electron fragments has allowed the structural characterisation of a number of novel σ-alane complexes. The incorporation of the transition metal fragments [Cp'Mn(CO)2] and [W(CO)5] permit comparison to archetypal borane and silane σ-complexes. Quantum chemical calculations suggest that the alane ligand has a binding energy close to that of dihydrogen but significantly less than that of CO, consistent with a predominant σ-donor role of the Al-H bond. The formation and structural characterisation of the κ2-complexes (OC)4M[κ2-H2AlDipp2NacNac] (M = Cr, Mo or W) define an unprecedented binding motif for the alane ligand. In the cases of chromium and molybdenum the κ2-complexes can be prepared either photolytically or via alkene displacement from the corresponding (OC)4M(cod) reagent. In the case of tungsten the alkene displacement route yields the desired product, but only under more forcing conditions. Spectroscopic characterisation of the related κ1-complex (OC)5Cr[κ1-H2AlDipp2NacNac], which readily forms the κ2-complex in solution without photolysis, has enabled the kinetics of chelate ring closure to be investigated. This analysis further characterises the formation of the unprecedented κ2-binding motif for the alane ligand.
14
Kennedy, Jennifer Louise. "Rapid microwave synthesis and characterisation of group 13 carbides." Thesis, University of Glasgow, 2015. http://theses.gla.ac.uk/6504/.
Повний текст джерелаАнотація:
This thesis describes the rapid microwave synthesis and subsequent structural characterisation of the group 13 carbides; specifically aluminium carbide, Al4C3 and boron carbide, typically B4C or B13C2. Due to practical considerations, which will be described in Chapters Three and Four, syntheses were conducted using elemental precursors. Using a multi-mode microwave cavity (MMC) with an operating frequency of 2.45 GHz it was necessary to make use of a sealed and inert environment for the synthesis of oxide-free products. This was rationalised by the high stability of the oxides of aluminium (for example, Al2O3 ΔH= -1675.69 kJ mol-1, Al4C3 ΔH= -206.9 kJ mol-1). For boron carbide, this observation was explained by the tendency for the oxides of boron to volatilise (for example as B2O3). The use of sealed, evacuated tubes facilitated the synthesis of high-purity carbide products in 30 minute timescales. This represents the first report of successful Al4C3 synthesis in a microwave cavity. In addition, the synthesis of boron carbide was achieved in air in just 90 seconds using a 2.45 GHz single-mode microwave cavity (SMC) for the first time. Following synthesis, products were characterised by powder X-ray diffraction (PXD), powder neutron diffraction (PND), Raman spectroscopy and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX). PXD was used for phase identification and preliminary structure refinement. Raman spectroscopy offered supporting information to PXD to confirm phase identity. SEM-EDX offered an insight into product morphology, for example, as a function of time, microwave power and cavity type, along with quantitative purity information. There was no PXD or EDX evidence for oxygen contamination across carbide samples. PND was used to probe defect structure and structural stability at elevated temperature. Microwave synthesised Al4C3 was structurally stable up to 1000 °C and boron carbide up to 400 °C (the maximum temperatures of the respective experiments). Aluminium carbide is reported elsewhere to interact with water. Some initial experiments surrounding the nature of this interaction have been conducted. The preliminary results have indicated potential for intercalation of water into the aluminium carbide structure. Obtaining a definitive structural model for boron carbide is complicated by the difficulty in distinguishing between boron and carbon experimentally. Boron and carbon are neighbours in the periodic table and near-isoelectronic. This complicates characterising the boron-carbon system by PXD, since PXD is mediated by electrons. There are also challenges posed by the system when using PND. The 10B isotope has an extremely high absorption cross section for neutrons; 3835.0(9) barn for 2200 m s-1 neutrons. In addition, the bound coherent neutron scattering length of 11B is very similar to that of carbon; C: 6.6460 fm and 11B: 6.65 fm. In this thesis, natural boron (abundance typically ~80% 11B and 20% 10B) was used to prepare boron carbide for PND experiments. By taking advantage of the contrast in scattering lengths of carbon and 10B, while obtaining high quality data by the presence of the non-absorbing isotope 11B, it was possible to derive a structural model for microwave-synthesised boron carbide. It is expected that the synthetic methods developed in this thesis can be applied to more complex carbide systems and beyond. A particularly encouraging result from this work is the feasibility of synthesising high-purity, crystalline boron carbide in 90 second timescales in open air. Such a synthesis would be compatible with an SMC based continuous flow process which may offer a step reduction in energy usage compared to conventional batch processes.
15
Mensinger, Zachary Lee 1982. "Synthesis and characterization of tridecameric Group 13 hydroxide clusters." Thesis, University of Oregon, 2010. http://hdl.handle.net/1794/11300.
Повний текст джерелаАнотація:
xx, 153 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number.In the research area of Group 13 hydroxide clusters, progress is often hampered by difficult and inefficient synthetic procedures. This has greatly limited the numerous potential applications of Group 13 hydroxide compounds, many of which require large amounts of material. Most relevant to this dissertation is their application as precursors for high quality amorphous metal oxide thin films. Addressing this issue, this dissertation presents a series of Group 13 containing hydroxide compounds of general formula [M 13 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 which are generated through an efficient, scalable synthetic procedure. Throughout this dissertation, the compounds are generally referred to by their metal content, i.e. [Ga 13 (μ 3 -OH) 6 (μ-OH) 18 (H 2 O) 24 ](NO 3 ) 15 is designated as Ga 13 . Chapter I reviews the literature of inorganic and ligand-supported Group 13 hydroxide compounds with the aim of identifying common structural trends in metal composition and coordinating ligands. This summary is limited to clusters of aluminum, gallium, and indium. Chapter II describes in detail the synthesis and characterization of one such cluster, Al 13 . Following this in Chapter III is the description of the first heterometallic Group 13 hydroxide compound, Ga 7 In 6 , which along with Ga 13 was used as a precursor material for metal oxide thin films in collaboration with Professor Doug Keszler at Oregon State University. Chapter IV describes a series of six Ga/In compounds, as well as two Al/In compounds. Included in this chapter is an analysis of the heat-induced decomposition properties of the Ga/In clusters. Understanding such thermal decomposition is particularly relevant for the use of these compounds as precursor materials, as an annealing step is used to condense the films. Chapter V addresses the potential for post-synthetic modification of the compounds through metal and ligand exchange reactions, an area that also addresses the issue of solution stability of the structures Chapter VI describes the synthesis and characterization of related Group 13 compounds, including two infinite chain structures and additional heterometallic compounds. Lastly, Chapter VII concludes this dissertation and discusses potential areas of future research. This dissertation includes co-authored material and previously published results.
Committee in charge: Victoria DeRose, Chairperson, Chemistry; Darren Johnson, Member, Chemistry; James Hutchison, Member, Chemistry; Michael Haley, Member, Chemistry; Raghuveer Parthasarathy, Outside Member, Physics
16
Hair, Gregory Scott. "Synthesis, structure and reactivity of group 13 Lewis acids and group 4 metallocene zwitterions /." Digital version accessible at:, 1999. http://wwwlib.umi.com/cr/utexas/main.
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Schröder, Anna Katharina. "The maximal subgroups of the classical groups in dimension 13, 14 and 15." Thesis, University of St Andrews, 2015. http://hdl.handle.net/10023/7067.
Повний текст джерелаАнотація:
One might easily argue that the Classification of Finite Simple Groups is one of the most important theorems of group theory. Given that any finite group can be deconstructed into its simple composition factors, it is of great importance to have a detailed knowledge of the structure of finite simple groups. One of the classes of finite groups that appear in the classification theorem are the simple classical groups, which are matrix groups preserving some form. This thesis will shed some new light on almost simple classical groups in dimension 13, 14 and 15. In particular we will determine their maximal subgroups. We will build on the results by Bray, Holt, and Roney-Dougal who calculated the maximal subgroups of all almost simple finite classical groups in dimension less than 12. Furthermore, Aschbacher proved that the maximal subgroups of almost simple classical groups lie in nine classes. The maximal subgroups in the first eight classes, i.e. the subgroups of geometric type, were determined by Kleidman and Liebeck for dimension greater than 13. Therefore this thesis concentrates on the ninth class of Aschbacher's Theorem. This class roughly consists of subgroups which are almost simple modulo scalars and do not preserve a geometric structure. As our final result we will give tables containing all maximal subgroups of almost simple classical groups in dimension 13, 14 and 15.
18
Gatlin, Jason Trevor. "Synthesis and characterization of novel group 13 tridecameric inorganic nanoclusters /." Connect to title online (Scholars' Bank) Connect to title online (ProQuest), 2007. http://hdl.handle.net/1794/6196.
Повний текст джерелаАнотація:
Thesis (Ph. D.)--University of Oregon, 2007.Typescript. Includes vita and abstract. Includes bibliographical references (leaves 233-262). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.
19
Tang, Christina Yuk Ching. "Synthesis and study of molecular compounds of Group 13 metals." Thesis, University of Oxford, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.393995.
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20
Basharat, Siama. "Precursor Synthesis and Chemical Vapour Deposition of Group 13 Oxides." Thesis, University College London (University of London), 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.487670.
Повний текст джерелаАнотація:
This thesis is primarily concerned with the precursor synthesis and chemical vapour deposition of group 13 oxides. The gas sensing properties of some of the films prepared have also been investigated. Chapter 1 gives an introduction to techniques used for deposition, in particular chemical vapour deposition (CYD). Chapter 2 describes the synthesis of gallium and indium alkoxides incorporating donor functionalised ligands. The donor-functionalised alkoxides [R2M(OR,)h (M =Ga, R = Et; M = In, R = Me; R' = CH2CH2NMe2, CH(CH2NMe2h CH2CH20Me, CH(CH3)CH2NMe2, C(CH3hCH20Me) were synthesised by the 1 : I reaction of R3M with R'OH in toluene at room temperature. Gallium and indium bis-alkoxides [RM(OR')2] (M =Ga, R =Et; M =In, R =Me; R' = CH2CH2NMe2, CH(CH2NMe2)2, CH2CH20Me, CH(CH3)CH2NMe2, C(CH3hCH20Me) have also been synthesised by the I : 6 reaction of R3M with R'OH i.n toluene under reflux conditions. Homoleptic gallium trisalkoxides [Ga(ORhh have been prepared by the I : 6, reaction of [Ga(NMe2hh with R'OH. Decomposition of all the compounds have been studied by thermal gravimetric analysis in Chapter 3. The formation of thin-films of gallium oxide 'via single-source low pressure chemical vapour deposition (LPCYD) methodology was investigated including detailed film growth studies and characterisation. The compounds described above were used as precursors and deposition was achieved at 550°C. Chapter 3 also investigates the formation of thin-films of gallium and indium oxide using aerosol assisted chemical vapour deposition (AACYD). This involved the ill situ reaction of [Ga(NMe2hh or R3M with a donor functionalised alcohol (R'OH). Gas sensing experiments on selected Ga203 films deposited by AACVD are described in Chapter 4.
21
Ewing, Sarah Jane. "Synthesis, crystal structures and properties of novel group 13 selenides." Thesis, Heriot-Watt University, 2014. http://hdl.handle.net/10399/2803.
Повний текст джерелаАнотація:
Solvothermal (and ionothermal) synthesis has been used in this work to prepare novel group 13 selenide materials. The new phases were characterised using single crystal and powder X-ray diffraction, spectroscopic methods (infrared and UV-Vis diffuse reflectance spectroscopy) and thermal analysis (thermogravimetric and elemental analysis). Other characterisation methods used include SQUID magnetometry and the measurement of optical properties. The effect of the structure directing organic molecule on the inorganic structure was investigated in this thesis, with a variety of novel materials synthesised. A family of one-dimensional chains have been prepared. The first, composed of fused four-membered rings, was found in [NH4][InSe2] (using 3,5-lutidine) and in a number of phases prepared with bicyclic superbases. The second chain-type, composed of fused four- and five-membered rings was found in [C6H16N2][Ga2-xInxSe3(Se2)] (0 < x < 2) and [C7H14N3][In2Se3(Se2)]. These chains contain a (Se2)2- perselenide bond, which was previously unreported for solvothermally prepared group 13 selenides. The third chain type, found in [C7H13N2][InSe(Se2)] and [C9H17N2][InSe(Se2)], contains fused five-membered rings. More complex one-dimensional ribbons were also prepared with superbases. Many two-dimensional layered phases have been prepared in this work. [NH4][InSe2], which contains supertetrahedral clusters, generates a second harmonic generation response. A novel phase which incorporated a transition metal into the structure has been found for [Mn(C6H14N2)3][H2O][(C6H14N2)2MnIn3(SH)2Se4.89(Se2)0.12]2. The novel hybrid gallium selenides, [Ga6Se9(C6H14N2)4][H2O] and [C6H14N2][Ga4Se6(C6H14N2)2] were also isolated. The novel layers in [C7H10N][In3Se5], contain a new octahedral building-block. A further layered material, [C8H12N][In3Se4.85(Se2)0.15] was prepared, where disorder of selenium was observed. Using weakly basic pyridine and its related methyl-substituted isomers (lutidines and picolines), a three-dimensional framework [C5H6N][In9Se14], was prepared and its ion-exchange capabilities studied. Further framework materials prepared in this work include: [enH2][NH4][In7Se12], [C6H14N2][(C6H12N2)2NaIn5Se9] and [In14Se21(Se2)3]6-. Using an ionothermal route, the known three-dimensional framework, [In33Se56]13- was prepared. The first indium selenide prepared using an ionic liquid, in this case, 1-ethyl-3-methyl-imidazolium bromide (EMIm-Br).
22
Gatlin, Jason Trevor 1976. "Synthesis and characterization of novel group 13 tridecameric inorganic nanoclusters." Thesis, University of Oregon, 2007. http://hdl.handle.net/1794/6196.
Повний текст джерелаАнотація:
xix, 262 p.Tridecameric inorganic hydroxo/aquo nanoclusters comprise a very small fraction of compounds under the large and varied umbrella of inorganic clusters. The Anderson-Evans cluster is a subset of these larger polymetallic tridecameric clusters. A novel synthesis of M 13 nanoclusters containing the Anderson-Evans cluster as cores has been discovered. This synthesis proceeds with the aid of a key organic reagent, which reacts with the nitrate counter anions of the starting material removing them from the solution. This forces the formation of a higher nuclearity species. Research continues to focus on the generality of the reaction as it applies to both inorganic and organic synthesis, as well as on extensive characterization of the novel clusters by a variety of analytical methods. These nanoelusters have proven to be useful as single-source precursors for the preparation of thin film oxides due to their high purity and crystallinity. Chapter I is a literature review of Anderson-Evans clusters in the context of how they comprise the core substructure in the reported tridecameric nanoclusters. Attention is also given to the numerous clusters or complexes that are absent from this series. Chapter II chronicles the discovery and synthesis of [Ga 13 (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 ](NO 3 ) 15 a nanocluster previously thought to be unstable. Chapter III describes the modification of the reaction to prepare other tridecameric inorganic nanoclusters with increases in yield and purity. Chapter IV reports the isolation of a series of new heterometallic tridecameric nanoclusters and a potential predictive strategy for tuning the metal ratios in the crystalline products. Chapter IV also highlights the application of the nanoclusters as precursors to thin film oxides. Initial characterization of tridecameric inorganic nanoclusters using powder and single crystal XRD, NMR, ToF-SIMS, EPMA and SEM instrumentation is explained in Chapter V. Finally, Chapter VI is a summary and a report of the current standing of a different project aimed at developing a template-assisted self-assembly of organic nanocages using two different ligand classes that were explored. This dissertation includes previously published and co-authored material.
Adviser: Darren W. Johnson
23
Ballabio, Claudio. "Establishment and analysis of patient-specific Group 3 medulloblastoma mouse models." Doctoral thesis, Università degli studi di Trento, 2020. http://hdl.handle.net/11572/262561.
Повний текст джерелаАнотація:
Medulloblastoma (MB) is the most common pediatric brain tumor with high morbidity and mortality. Among the four major MB groups, patients with Group3 MB currently have the worst outcome and nearly 50% are metastatic at the time of diagnosis. However, the molecular mechanisms underlying Group 3 MB are still unknown. Exploiting in vivo transfection of mouse cerebellar cells, we tested different patient- specific combinations of genes for their ability to induce Group 3 MB in mice. We identified Otx2 and cMYC as strong inducers of tumors faithfully recapitulating human Group 3 MB.
To identify a druggable signaling pathway, we analyzed sequencing data of human patients harboring Otx2/cMYC overexpression. Among all the putative oncosuppressors, SMARCA4 is the most frequently mutated. Indeed, co-expression of SMARCA4 with Otx2 and cMYC is able to block tumorigenesis, through regulation of CDKN2B and CRABP1 expression. Interestingly, patient-specific SMARCA4T910M mutant is able to block wild- type SMARCA4 effects in a dominant-negative manner. Since SMARCA4 has an antagonistic relationship with histone methyltransferase EZH2, we used EZH2-inhibitors to recapitulate SMARCA4 antitumorigenic effects.
Little is known about Group 3 MB developmental origin and several embryonic mouse cerebellar progenitors have been proposed as possible cell of origin. Here, we found that in postnatal mouse cerebellum, the S100b+ cells are competent to induce medulloblastoma while Math1, Sox2 and Ascl1 positive cells seem to be unresponsive to oncogenic insults. Taken together, our data suggest that the competency of different cells to develop MB could change during brain development, depending on their developmental stage and cellular identity.
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Marchant, Sarah. "Synthesis and characterisation of some novel derivatives of group 13 metals." Thesis, University of Oxford, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.418482.
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Pickett, Nigel Leroy. "Synthetic and structural aspects of Group 13 and 15 element chemistry." Thesis, University of Newcastle Upon Tyne, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.238813.
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Lawson, Yvonne Gayle. "Synthetic and structural studies involving group 13, 15 and 17 elements." Thesis, University of Bristol, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263828.
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Tate, Christopher William. "'Ate compounds incorporating lithium and a group 12/13 Lewis acid." Thesis, University of Cambridge, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.614101.
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Knapp, C. E. "Synthesis, chemical vapour deposition and structural studies of group 13 alkoxides." Thesis, University College London (University of London), 2010. http://discovery.ucl.ac.uk/20176/.
Повний текст джерелаАнотація:
This work is concerned with the synthesis of precursors to group 13 oxide thin films, and the subsequent chemical vapour deposition (CVD) of group 13 mixed metal oxide films. Investigations into the mechanisms at work during their decomposition via various techniques including gas phase electron diffraction (GED) is also discussed. A wide variety of group 13 alkoxides have been synthesised and characterised and described in this thesis. Significant findings support previous investigations showing the reaction of trialkyl group 13 complexes [MR3] with an excess of a donor functionalised alcohol does not yield a group 13 bis(alkoxide). However, compounds of the type [Ga(OR)nCl3-n] (n = 1, 2) have been synthesised using direct routes from gallium amido precursors, which are also described herein. In addition a wide variety of novel group 13 precursors incorporating a mixture of ligands leading to enhanced properties, desirable for CVD are presented. The gas phase structures of the dimethylalkoxygallanes, [Me2GaOCH2CH2NMe2]2 and [Me2GaOCH2CH2OMe]2 have been obtained via gas-phase electron diffraction from studying the vapour produced upon heating. Ab initio molecular orbital calculations are presented for these compounds, as well as the gas phase structure of [Me2GaOtBu]2. Only the monomeric forms [Me2GaOCH2CH2NMe2] and [Me2GaOCH2CH2OMe] are observed in the gas phase with donor functionalised ligands, whereas the dimer [Me2GaOtBu]2 remains intact in the gas phase. Gallium oxide films were grown via AACVD using a variety of group 13 precursors. The films deposited were not oxygen deficient and little carbon contamination was observed, which is attributed to being a direct result of precursor design. Thin films of indium gallium oxide, and zinc gallium oxide were also produced from the in situ reactions of InMe3, GaMe3 and HOCH2CH2OMe (for GaxIn2-xO3) and ZnEt2, GaMe3 and HOCH2CH2OMe (for GaxZnyO) via AACVD on silica substrates.
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Bunn, Natalie R. "Synthetic and structural studies of low coordinate group 13 ligand systems." Thesis, Cardiff University, 2005. http://orca.cf.ac.uk/56114/.
Повний текст джерелаАнотація:
A new generation of diode lasers is being developed using quantum dots as the gain generating medium. A detailed understanding of the carrier recombination mechanisms and optical gain generation is essential for optimisation of their performance. The aim of this work is to further understand the optical processes occurring in quantum dots. In particular, the effect of the localisation of the energy states in the dots on the recombination mechanisms and the gain/absorption is studied. It is often assumed that the rates of nonradiative recombination via defects, radiative recombination and Auger recombination are proportional to linear, quadratic and cubic functions of the carrier number respectively. The derivation of these functional forms is possible in quantum well and bulk structures because the extended electronic states make it meaningful to talk of a global carrier population. In a quantum dot system the dependence of the recombination processes on the total number of electrons populating the dots is modified by the localisation of all the recombination processes. In this thesis a computer model has been developed in which the dots are occupied by integer numbers of electrons and holes, with electron and hole occupancies controlled by Fermi-Dirac statistics. The recombination processes have similar dependences on the electron number and there is no clear transition from one process to another as the injection level is increased. These dependences cannot be represented by simple power law functions of the carrier number. An alternative model, in which each dot is electrically neutral, has also been studied, and the two models show significant differences for the hole distribution as the injection is increased. It is found that analyses based on power law relations between recombination rates and carrier number, as used for extended state systems, cannot be applied to localised recombination in dots.
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Himmel, Hans-Jörg. "Generation and characterisation of some molecular compounds of the group 13 metals." Thesis, University of Oxford, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365869.
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Kloth, Marc. "Studies of low oxidation state group 13 halide, hydride and heterocyclic complexes." Thesis, Cardiff University, 2004. http://orca.cf.ac.uk/54540/.
Повний текст джерелаАнотація:
The work presented in this thesis describes the synthesis, structure and stability of a range of halido, hydrido and heterocyclic complexes of the group 13 elements. The underlying theme is the synthesis of low valent group 13 complexes. The work upon this subject is divided into five chapters. Chapter 1 provides a general introduction to the members of group 13 and to low oxidation state group 13 halide chemistry. The history of binary group 13 metal trihydride complexes and the reasons behind their inherent instability are also discussed. Chapter 2 details the use of a stable nucleophilic N-heterocyclic carbene, l,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene. (IPr), and nitrogen donor ligands, namely a bulky diazabutadiene (Ar-DAB), Ar = 2.6-Pr'2C6H3. quinuclidine and formamidinate, in the formation of group 13 trihalide complexes. A series of metal trihalide complexes have been prepared and characterised, e.g. InBr3(L) . L = IPr or Ar-DAB, whose reduction reactions with alkali metals did not yield low valent metal metal bonded group 13 species. In addition, the reactivity of "Gal" towards pyridine based ligands is described: 'Gal* reacts, for example, with 2.2'-bipyridine (bipy) to give salts of composition Ga(bipy)3 I 3, ((bipy)2Ga}2(u-OH)2 : Ga2l6 l 6 or {(bipy)2Ga 2(u-OH)2 I 4. depending upon the reaction conditions. All new compounds have been crystallographically characterised. Chapter 3 introduces the reactivity of diazabutadienes (Ar-DAB or Bul-DAB) towards low oxidation state group 13 iodides which afforded, for example, the paramagnetic compounds. {IGa(But-DAB)}2, I2Al(Ar-DAB) and {CHn(Ar-DAB)}2 which have been characterised by X-ray crystallography and EPR spectroscopy. In addition, the synthesis of the second example of an anionic gallium(I) N-heterocyclic carbene analogue. {(TMEDA)KGa(Ar-DAB)}2, is described. This complex displays a Ga Ga interaction in the solid state which is unprecedented for this complex type. Chapter 4 lists reactivity studies of a new gallium(I) carbene analogue, {(TMEDA)KGa(Ar-DAB)} 2. towards main group halide complexes. These studies led to some decomposition products which are paramagnetic and have been studied both crystallographically and by EPR spectroscopy. The reactivity of the gallium carbene analogue towards sources of oxygen has been investigated and the complex, ((u-0)Ga(Ar-DAB)2}2 2 from the reaction with N2O. has been isolated and structurally characterised. In addition, an unprecedented 7t-cyclopentadienyl bridged digallane complex, {Ga(Ar-DAB)2h{u-CpK(TMEDA)2}. incorporating the first structurally characterized -interaction with a Ga(II) center, results from the oxidative coupling of an anionic gallium(I) heterocycle with cyclopentadienyl thallium(I). Chapter 5 introduces the known hydride chemistry of indium and describes the synthesis of a number of novel group 13 hydride complexes. These include the preparation and characterisation of the first examples of amido indium hydride complexes, one of which has unprecedented thermal stability. In addition, these studies led to the first covalently bonded metal complexes derived from an anionic gallium carbene analogue, one of which, InH2{Ga(Ar-DAB)}2 Li(TMEDA)2, contains the first example of a structurally authenticated In Ga bond. This chapter also includes the preparation and characterisation of a subvalent pentaindium cluster compound.
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Zhao, Yue. "Preparation and investigation of group 13 metal organo-phosphate hybrid-framework materials." Winston-Salem, NC : Wake Forest University, 2009. http://dspace.zsr.wfu.edu/jspui/handle/10339/42608.
Повний текст джерелаАнотація:
Thesis (Ph.D.)--Wake Forest University. Dept. of Chemistry, 2009.Title from electronic thesis title page. Thesis advisor: Abdessadek Lachgar. Vita. Includes bibliographical references (p. 140-156).
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Gorden, John David. "Low valent and mixed valent cyclopentadienyl complexes of the group 13 elements." Access restricted to users with UT Austin EID Full text (PDF) from UMI/Dissertation Abstracts International, 2001. http://wwwlib.umi.com/cr/utexas/fullcit?p3036602.
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Rege, Francis Mark de. "Zirconium-group 13 heterobinmetallic compounds and the synthesis of oxysulfides in sodium polysulfide." Thesis, Massachusetts Institute of Technology, 1996. http://hdl.handle.net/1721.1/38778.
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Coombs, Natalie D. "Synthesis of low-coordinate transition metal complexes of the heavier group 13 elements." Thesis, Cardiff University, 2008. http://orca.cf.ac.uk/54759/.
Повний текст джерелаАнотація:
This thesis describes the synthesis, structural and reaction chemistry of a number of novel gallium and indium containing species, including metal complexes featuring previously unreported gallium and indium ligand systems. The synthesis, spectroscopic and structural characterisation of the asymmetric haloindyl (n5-C5R5)Fe(CO)2In(Mes*)Br (R = H, Me) and halogallyl Cp*Fe(CO)2Ga(Mes)I complexes are reported herein, with Cp*Fe(CO)2ln(Mes*)Br representing the first example of structurally characterised asymmetric bromoindyl complex. Cp*Fe(CO)2In(Mes*)Br is a versatile substrate for the synthesis of asymmetric indyl complexes via substitution chemistry, thereby allowing the synthesis and characterisation of Cp*Fe(CO)2In(Mes*)ERn (ERn = OC6H4/Bu-4, SPh). The synthesis, spectroscopic and structural characterisation of the dihalogallyl complex Cp*Fe(dppe)Gal2 is also reported this synthesis was accomplished via photolytic displacement of the carbonyl ligands in Cp*Fe(CO)2Gal2 2 by dppe 1,2-bis(diphenylphosphino)ethane. Cp*Fe(dppe)Gal2 has proven to be versatile reagent in the generation of the asymmetric halogallyl species via substitution chemistry with retention of the iron-gallium bond, thereby allowing the synthesis and characterisation of Cp*Fe(dppe)Ga(Mes)I. The diiodogallyl complex has also been implicated in the synthesis of the first structurally characterised base-free cationic gallylene complex Cp*Fe(CO)2Gal + BAr/4 bearing a terminally bound Gal ligand which is valence isoelectronic with CO and N2. Investigations into the synthesis of molybdenum- and ruthenium-phosphine containing systems are also reported herein. Insertion of 'Gal' into metal-halogen bonds has proved to a viable synthetic route, for example in the 7 7 formation of (n-C7H7)Mo(CO)2Gal2 2. Further reaction of (n-C7H7)Mo(CO)2Gal2 2 with dppe, however, has been shown to yield (r - C7H7)Mo(CO)2Gai2 2(u-dppe). Investigation of 'Gal' insertion reactions involving ruthenium-halogen bonds have shown to yield the tetraiodogallate species CpRu(PPh3)2(u-I)Gal3 and CpRu(dppe) Gal4. The synthesis, spectroscopic and structural characterisation of the bridging halo-indanediyl complexes Cp*Fe(CO)2 2lnX (X = Br, I) are reported. The bromo-substituted species has proven to be a useful precursor in the synthesis of the cationic trimetallic system {Cp*Fe(CO)2}2(-In) + BA/4, the formation of which has been shown to be strongly dependant on the nature of abstracting agent and on the identity of the halide. Reactivity studies of {Cp*Fe(CO)2}2( i-E) + (E = Ga, In) involving the addition of nucleophiles has allowed the synthesis and characterisation of the three-coordinate cationic complexes {Cp*Fe(CO)2}2(u-E L) + BAr4 (E = Ga, In L = thf, 4-picoline, PPh3). The syntheses and metallation of sterically bulky carbazol-9-yl ligands derived from 1,8-diaryl-3,6-dimethylcarbazole are described herein. Furthermore, the synthesis and structural characterisation of the amidogally l complexes (1,8-diphenyl-3,6-dimethylcarbazol-9-yl)gallium dichloride and (1,8-dimesity 1-3,6-dimethylcarbazol-9-yl)gallium dichloride are reported by salt metathesis reactions involving gallium trichloride. Investigations of subsequent reduction chemistry using potassium metal yielded the potassium salt 1,8-diphenyl-3,6-dimethylcarbazol-9-yl-potassium. Quantum chemical investigations using Density Functional Theory have been explored to probe the electronic structure in the novel bond types. In particular, studies targeted factors affecting the degree of 7c back-bonding (and hence multiple bond character) within the TM-ER bond.
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Rossin, Andrea. "Synthetic and computational studies of organometallic complexes containing low-coordinate group 13 ligands." Thesis, Cardiff University, 2004. http://orca.cf.ac.uk/55933/.
Повний текст джерелаАнотація:
The work presented in this thesis is concerned with synthetic and computational studies of low coordinate transition metal complexes of boron. New symmetrically bridged boryl complexes of iron and manganese have been prepared and characterised. Information obtained from spectroscopic and structural analyses, together with Density Functional theoretical studies, has been used to investigate the nature of the metal-boron bonds in these complexes. Development of the chemistry of related terminal analogues has also been undertaken. The M-B bonds present in these molecules can be considered mainly o in character, with very little n contribution. Attempts to investigate the chemistry of base-stabilised boryl complexes, using PMe3 and THF as Lewis bases, shows that, while PMe3 adducts with haloboranes are very stable and do not react with metallic fragments, THF complexes give more promising results, especially when THF is also used as a solvent for the reaction. Substitution and abstraction chemistry of the new (mesityloxy)chloroborane (MesO)BCl2 has been analysed. Replacement of the chlorine atom in (ti5-C5H5)Fe(CO)2 B(OMes)Cll by other nucleophiles is possible, thereby generating new asymmetric boryl ligands. Chloride abstraction using NalBAr'J leads to the formation of the fluoroboryl complex (Tf-C5Hs)Fe(CO)2 B(OMes)F possibly via the putative terminal borylene (n5-C5R5XCO)2Fe=B(OMes) Oxidative addition of B-H, B-B and B-X bonds to both d-block (Rh, Pt) and p-block (In, Sn) metals as an alternative pathway to boryl complexes has also been examined. Unfortunately, while many of the reactions appear to give the expected products (on the basis of in situ NMR monitoring), purification difficulties have prevented the isolation of many of these species as pure compounds. DFT studies on terminal boron- aluminium- and gamum containing complexes have been undertaken. Geometry optimisation, molecular orbital composition, bond dissociation energies and bond density partitioning have been investigated in order to probe the nature of the M=E bonds (E = B, Al, Ga) and the dependence of compound stability on both the ancillary metal-bound ligands and on the substituent of the group 13 diyl fragment. The examples considered were diyl complexes of general formula (n5-C5R5KL)2M(EX)1D+, the "naked" bridging gallium complex ({(CrMes)Fe(CO)2}2Ga + and five gallium carbene complexes of first row transition metals (V, Mn, Fe, Co, Ni), featuring the heterocyclic ligand {:Ga N(Ph)CH 2}.
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Normand, Mickaël. "Group 13 organometallic chemistry and macromolecular catalytic engineering for polymers issued from bioresources." Rennes 1, 2012. http://www.theses.fr/2012REN1S091.
Повний текст джерелаАнотація:
Poly(lactic acid) (PLA) is a biocompatible and biodegradable polymer produced by ring-opening polymerization (ROP) of lactide (LA), which is used in a wide-range of applications. A large number of highly efficient catalysts/initiators have been introduced, such as alkoxides of Al, Zn and rare-earth metals. For instance, aluminium catalysts/initiators have been extensively exploited for the ROP of rac-LA to provide remarkable control over molecular weights and polydispersities, good stereocontrol being achieved in some cases. At the same time, due to very specific synthetic chemistry the ROP precursors incorporating indium still remain rare. We report in this thesis five main chapters dealing with the following topics: i) synthesis of new indium complexes of fluorinated dialkoxy-diimino salen-like ligands and their use in the ROP of rac-LA; ii) preparation of new {phenoxy-imine}-aluminum and indium complexes and their catalytic properties in the immortal ROP of lactide; iii) synthesis of new bimetallic aluminum and indium initiators supported by bis(phenoxy-imine) ligands and their use in the ROP of rac-LA; iv) Meerwein-Pondorf-Verley reduction processes in aluminum and indium isopropoxide complexes of imino-phenolate ligands; v) cyclodextrin-centered polyesters: controlled ROP of cyclic esters from beta-cyclodextrinLe poly(acide lactique) (PLA) est un polymère biocompatible et biodégradable dont les applications sont très diverses et qui est principalement produit par polymérisation par ouverture de cycle (ROP) du lactide (LA). Un grand nombre de catalyseurs/initiateurs particulièrement efficaces ont été synthétisés au cours des trente dernières années, tels que les dérivés alcoxy d'aluminium, de zinc et de métaux des terres rares. Par exemple, les catalyseurs/initiateurs à base d'aluminium furent largement exploités pour la ROP du lactide racémique (rac-LA) pour conduite à de remarquables contrôles des masses moléculaires et des distributions de masses ainsi qu'à un bon contrôle de la stéréochimie du polymère final. Encore aujourd'hui, en raison de voies de synthèses chimiques très spécifiques, les exemples de ROP du lactide impliquant des catalyseurs/initiateurs à base d'indium restent rares. Ainsi, nous reportons dans ce manuscrit de thèse cinq principaux chapitres traitant des sujets suivants : i) synthèse de nouveaux complexes d'indium supportés par des ligands dialcoxy-diimino fluorés de type hémi-salen and leur utilisation en ROP du rac-LA ; ii) préparation de nouveaux complexes {phenoxy-imine} d'aluminium et d'indium et leur propriétés catalytiques en ROP immortelle du lactide ; iii) synthèse de complexes bimétalliques d'aluminum et d'indium supportés par des ligands bis(phenoxy-imine) et leur utilisation en ROP du rac-LA ; iv) processus de réduction de type Meerwein-Pondorf-Verley dans des complexes isopropylate imino-phenolate d'aluminum et d'indium ; v) synthèse de polyesters centrés sur la béta-cyclodextrine par ROP contrôlée d'esters et de carbonate cycliques
38
Berman, Aaron. "Memento Mori." Pitzer College, 2007. http://ccdl.libraries.claremont.edu/u?/stc,13.
Повний текст джерелаАнотація:
Animated color film with images of water, birds, winged humans, a man in a hooded sweatshirt, doors, the sea, a woman on a stool wearing a red scarf, marching soldiers, a gun, a knife, blood on hands, a dancing couple, a crowd of dancers, a seed, plants growing, clouds, a flying winged person, a figure playing an instrument. The images transform into each other in ever-changing sequences.
39
Peckermann, Ilja [Verfasser]. "Neutral and Cationic Complexes of Group 13 Metals: Synthesis, Characterization, and Reactivity / Ilja Peckermann." Aachen : Shaker, 2010. http://d-nb.info/109804102X/34.
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Simpson, Linda. "Trivalent group 13 metal complexes of N-substituted-3-hydroxy-2-methyl-4-pyridinones." Thesis, University of British Columbia, 1990. http://hdl.handle.net/2429/28885.
Повний текст джерелаАнотація:
The compounds tris(N-ռ-propyl-3-hydroxy-2-methyl-4-pyridinonato) aluminum(III), -gallium(III), and -indium(III) and tris(N-ռ-butyl-3-hydroxy-2-methyl-4-pyridinonato)aluminum(III), -gallium(III), and -indium(III) were synthesized. All six compounds were prepared via the metal template effect. They were characterized by IR, FAB-MS, ¹H NMR, ²⁷Al NMR, and elemental analysis. Three of the six complexes were studied by single-crystal X-ray diffraction. They formed trihydrates, unlike their N-methyl and N-ethyl analogues, which formed dodecahydrates. The ռ-butyl complex Al(C₁₀H₁₄N0₂)₃‧3H₂0 (1) and ռ-propyl complexes Al(C₉H₁₂N0₂)₃‧3H₂0 [2], and Ga(C₉H₁₂N0₂)₃‧3H₂0 {3} were basically isostructural, crystallizing in the space group P3 with the following crystal parameters for 1, [2], and {3}: α= 15.885 (1) ([15.328 (1)], {15.367 (2)}) Å, c = 7.280 (8) ([7.2321 (2)], {7.256 (2)}) Å, Z = 2. The data were refined by using 1280 ([1377], {1802}) reflections with I>3σ(I) to R and Rա values of 0.047 ([0.057], {0.055)) and 0.061 ([0.077], {0.081}), respectively. The complexes exist as the rigidly fac geometries with infinite chains of hydrogen bonds parallel to the c axis.Science, Faculty of
Chemistry, Department of
Graduate
41
Fergani, Hadi. "Metal-atom-mediated chemical transformations, the reaction of group 13 metal atoms with arenes." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape7/PQDD_0017/MQ46480.pdf.
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Sanderson, George. "Coordination complexes of Group 13 halides : towards a new class of PET imaging agents." Thesis, University of Southampton, 2015. https://eprints.soton.ac.uk/380909/.
Повний текст джерелаАнотація:
Reaction of the triaza macrocycles RMe2-tacn (R = Me, Bz) with the Group 13 chlorides MCl3 gives the solvent free distorted octahedral adducts [MCl3(RMe2-tacn)] (M = Al, Ga, In). Reaction of the trichloro complexes with aqueous KF at room temperature yields the hydrated complexes [MF3(RMe2-tacn)]∙xH2O. The trifluoro complexes are formed in high yield, are stable under a range of conditions, and display significant H-bonding interactions between the coordinated fluoride ligands and the crystallised water molecules in the solid state, confirmed crystallographically. The complex [GaCl3(BzMe2-tacn)] was successfully radiolabelled with aqueous K18F/19F at room temperature to give the complex [Ga18F19F2(BzMe2-tacn)] with 30% incorporation in 45 minutes. The purified compound is stable in phosphate buffered saline at pH 7.5 and represents an exciting alternative route towards the 18F radiolabelling of temperature sensitive biomolecules in PET imaging applications. The complex [GaF3(BzMe2-tacn)] can act as a metalloligand towards alkali metal and ammonium salts via coordination of the metal fluoride fragment. Crystallographic analyses show that this results in a series of unusual supramolecular assemblies with Li+, Na+ and K+. Reaction of Ga(NO)3∙9H2O with 1-benzyl-1,4,7-triazacyclononane-4,7-dicarboxylic acid hydrochloride (L∙HCl) gives the complex [GaCl(L)]∙2H2O. Treatment of this complex with carrier free 18F- at 80 ᵒC gives the radiolabelled complex [Ga18F(L)] in high yield. The compound may be purified by a cartridge based method. The purified compound is stable up to at least pH 6, but loses fluoride at neutral pH. Hydrothermal synthesis was used to access complexes of the poorly soluble hydrated Group 13 fluorides directly. Reaction of MF3∙3H2O (M = Al, Ga, In) with the tridentate imine ligand 2,2’,2’’-terpyridine gives the hydrated adducts mer-[MF3(terpy)]∙3H2O. The complexes display extensive H-bonding interactions in the solid state. Attempts to access the 18F labelled complex [Ga18F19F2(terpy)] via halide exchange from the preformed trichloro complex as an alternative complex type for potential use in PET imaging were not successful. Reaction of MF3∙3H2O with the bidentate imines 1,10-phenanthroline and 2,2′-bipyridine (L-L) under hydrothermal conditions gives the neutral complexes [MF3(L-L)(OH2)]. A number of alternative tacn based ligands incorporating amide pendant arm functionality were synthesised and characterised as potential future architectures for metal complexes used in imaging applications.
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Desat, Marcella E. [Verfasser], and Manfred [Akademischer Betreuer] Scheer. "Polynuclear Group 13 Compounds: Synthesis, Characterization, and Reactivity / Marcella E. Desat ; Betreuer: Manfred Scheer." Regensburg : Universitätsbibliothek Regensburg, 2020. http://d-nb.info/121748129X/34.
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Songsasen, Apisit. "Studies on microfibre formation from condensation of vapours of group 13 and 14 sub-oxides." Thesis, University of Bristol, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262737.
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Yanagisawa, Tatsuya. "Studies on Single-bond Compounds between Heavier Group 13/15 Elements toward Small Molecule Activation." Kyoto University, 2020. http://hdl.handle.net/2433/253112.
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Jacky, Alejandro Hernandez. "Inkin’, Taggin’, Flashin’, and Flowin’: Defining Group Identity Through Mara Salvatrucha Expressive Culture." The Ohio State University, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=osu1337881140.
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Chen, Xiaohui. "Optical stimulation of quantal exocytosis on transparent microchips." Diss., Columbia, Mo. : University of Missouri-Columbia, 2007. http://hdl.handle.net/10355/4890.
Повний текст джерелаАнотація:
Thesis (Ph. D.)--University of Missouri-Columbia, 2007.The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on January 30, 2008) Vita. Includes bibliographical references.
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Bloor, L. G. "On the synthesis and chemical vapour deposition of group 13 precursors towards metal oxide thin films." Thesis, University College London (University of London), 2012. http://discovery.ucl.ac.uk/1350197/.
Повний текст джерелаАнотація:
Various routes towards novel chlorogallium bis(alkoxides) and heteroleptic gallium alkoxides have been investigated. Compounds of the type, [GaCl(OR2)2] and [Ga(OR2)2(OR’)] (R = CH2CH2NMe2, CH2CH2NEt2, CH2CH2CH2NMe2; R’ = Me, Et, iPr, tBu), were synthesised using air sensitive methods and analysed by a variety of techniques. The chlorogallium bis(alkoxides) showed diastereotopic NMR splitting and in depth 1H NMR studies and DFT calculations were carried out on [GaCl(OCH2CH2CH2NMe2)2] to investigate the in situ ring conversion mechanism. Thermogravimetric analysis was employed to study the decomposition characteristics of the compounds, which were then used as single-source precursors towards gallium oxide thin films using aerosol-assisted chemical vapour deposition (AACVD). Amorphous, transparent films of Ga2O3 were deposited at 450 °C onto glass and quartz substrates. Subsequent annealing at 1000 °C gave crystalline films. Nitrogen-doped indium oxide films were deposited by AACVD via the in situ reaction of [In{NtBu(SiMe3)}3] and three equivalents of HOCH2CH2NMe2. The resultant films had a range of morphologies depending on solvent and temperature employed during the deposition. The cubic phase In2O3 films deposited had band gaps of ~2.9 eV suggesting nitrogen incorporation. These films were tested on steel and titanium substrates for their visible light water-splitting properties. Films were tested for their hydrogen production but limited activity as a photocatalyst was observed in the visible region. However, In2O3 nanoparticles produced using a solvothermal method and Ti- and Ta-doped In2O3 thin films grown via AACVD were tested for their gas sensing properties. Sensors were tested against reducing oxidising gases. The In2O3 nanoparticles showed the highest response to all gases, in particular ethanol. In2O3:Ta also showed a significant response to ethanol and smaller responses to other gases. Overall, novel precursors have been used as single-source precursors to main group oxide thin films, which were deposited via AACVD. Photocatalytic and gas sensing applications of these films have been explored.
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Kim, Sung Wook. "Synthesis of 13-Group Metal Oxides via Solvothermal Reaction and Control of the Pore Structure of Al2O3." 京都大学 (Kyoto University), 2010. http://hdl.handle.net/2433/120882.
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Perold, Mariechen Deirdre. "The prevalence of anxiety in a group of 7 to 13 year old learners in the Western Cape." Thesis, Stellenbosch : Stellenbosch University, 2001. http://hdl.handle.net/10019.1/52556.
Повний текст джерелаАнотація:
Thesis (MEdPsych)--University of Stellenbosch, 2001.ENGLISH ABSTRACT: A study of the relevant literature revealed anxiety disorders to be of the most prevalent psychiatric disorders of childhood. Prevalence is put at between1 % and 20% in different studies. The purpose of this study was to gather data regarding the prevalence of anxiety in a group of learners in the Western Cape. Literature regarding the different etiological theories of anxiety, the classification of anxiety disorders, their prevalence, the living conditions of the child in South Africa and the assessment of anxiety in children were explored. The study further examined DSM-IV defined anxiety disorder symptoms in a large community sample of 7 to 13 year old learners in the Western Cape. This was done by a simple survey approach, using quantitative measures. Two self-report questionnaires were used, ie the Spence Children's Anxiety Scale (SCAS) and the Screen for Child Anxiety Related Emotional Disorders (SCARED). Results showed that the psychometric properties of the SCAS and the SCARED were moderate (convergent validity) to sufficient (reliability). The original factor structure of the SCAS and the SCARED did not emerge in this sample of learners, although factor analysis did yield evidence of the presence of a number of the hypothesised anxiety categories (ie social phobia, panic disorder, fears and generalised anxiety disorder). Results also indicated that a high percentage of the subjects reported serious anxiety symptoms, namely 22% on the SCAS and 25.6% on the SCARED. The most common anxiety symptoms of the learners in the Western Cape pertained to generalised anxiety disorder, separation anxiety disorder, social phobia, and obsessive-compulsive disorder. Studying the content of the most common responses revealed that symptoms referring to compulsive behaviours and physical separation from the parents were frequent.
AFRIKAANSE OPSOMMING: 'n Studie van die relevante literatuur het aan die lig gebring dat angsversteurings van die mees algemene psigiatriese versteurings tydens die kinderjare is. Die voorkoms daarvan wissel tussen 1% en 20%, en die doel van hierdie studie was om data oor die voorkoms van angs by 'n groep leerders in die Wes-Kaap in te samel. Literatuur oor die verskillende etiologiese teorieë rakende angs, die klassifikasie van angsversteurings, die voorkoms daarvan, die lewensomstandighede van die kind in Suid-Afrika, en die assessering van angs, is ondersoek. Daarna is angsversteurings soos gedefinieer deur die DSM-IV, ondersoek in 'n groot steekproef vanuit die gemeenskap, van 7- tot 13- jarige leerders in die Wes-Kaap. Dit is gedoen deur van 'n eenvoudige opname ontwerp gebruik te maak, en deur kwantitatiewe metodes te gebruik. Twee vraelyste waarin die subjekte inligting omtrent hulself verskaf, is gebruik, naamlik die Spence Children's Anxiety Scale (SCAS) en die Screen for Child Anxiety Related Emotional Disorders (SCARED). Resultate het aangetoon dat die psigometriese eienskappe van die SCAS en die SCARED matig (die konvergerende geldigheid) en voldoende (die betroubaarheid) was. Die oorspronklike faktorstruktuur van die SCAS en die SCARED het nie na vore gekom in hierdie steekproef nie. Faktoranalise het egter die teenwoordigheid van 'n aantal gehipotetiseerde angskategorieë aangedui, naamlik sosiale fobie, paniekversteuring, vrese en algemene angsversteuring. Resultate het ook getoon dat 'n hoë persentasie van die respondente die teenwoordigheid van ernstige angssimptome aangedui het, naamlik 22% op die SCAS en 25.6% op die SCARED. Die mees algemene angssimptome by die leerders in die Wes-Kaap het te doen gehad met algemene angsversteuring, skeidingsangs, sosiale fobie en obsessief-kompulsiewe versteuring. Simptome watte doen het met kompulsiewe gedrag en fisiese skeiding van hulouers, het die populêrste geblyk te wees.