Molecular precursor approach to metal oxide and pnictide thin films

AbstractMolecular precursors for the preparation of main group metal oxide and transition metal pnictide thin films have been developed. This work involves the design and synthesis of single-source precursors that contain all the elements required in the thin film. Design of the ideal precursor presents a significant challenge since they must be volatile, non-toxic and thermally stable. Therefore the precursors have been tailored to give clean, reproducible decomposition leading to high quality thin films with good coverage of the substrate. In this review key aspects of precursor synthesis and thin film deposition developed in our group are described. The range of precursors developed for main group oxides, in particular gallium and indium oxide, are discussed, with the most studied being the donor-functionalized alkoxides of the type [R2M(OR′)]2 (M=Ga, In; R=H, Me, Et; R′=CH2CH2NMe2, CH2CH2OMe etc.). Preliminary mechanistic studies suggest that monomers are formed in the gas phase via stabilization of the metal centre by the donor atom (N or O). Precursors to transition metal pnictides have also been developed, including guanidinates, imides, phosphine and arsine compounds and an overview of their use in film deposition is given

Reactivity of vanadium oxytrichloride with [beta]-diketones and diesters as precursors for vanadium nitride and carbide

Vanadium(V) oxytrichloride was reacted with 2,4-pentanedione, diethyl malonate, and diethyl succinate under inert conditions, forming compounds: dichloro(oxo)(2,4-pentanedione) vanadium(V) [1], dichloro(oxo)(diethyl malonate) vanadium(IV) [2] and dichloro(oxo)(diethyl succinate) vanadium(IV) [3]. Compounds 1–3 are coordinated to the vanadium centre through the two carbonyl oxygen atoms of the bidentate ligand. It was determined by X-ray crystallography that the structures of the resulting complexes were significantly different, resulting in a monomeric complex (1), a tetrameric ring (2) and a 1D coordination polymer (3). Following the synthesis and isolation of 1–3, they were tested as precursors for vanadium nitride and vanadium carbide by annealing under nitrogen and argon respectively at 1200 °C for 24 h. The resulting materials were characterised by: XRD, EDS, XPS and TEM

Self-assembly of Microcapsules via Colloidal Bond Hybridization and Anisotropy

Particles with directional interactions are promising building blocks for new functional materials and may serve as models for biological structures. Mutually attractive nanoparticles that are deformable due to flexible surface groups, for example, may spontaneously order themselves into strings, sheets and large vesicles. Furthermore, anisotropic colloids with attractive patches can self-assemble into open lattices and colloidal equivalents of molecules and micelles. However, model systems that combine mutual attraction, anisotropy, and deformability have---to the best of our knowledge---not been realized. Here, we synthesize colloidal particles that combine these three characteristics and obtain self-assembled microcapsules. We propose that mutual attraction and deformability induce directional interactions via colloidal bond hybridization. Our particles contain both mutually attractive and repulsive surface groups that are flexible. Analogous to the simplest chemical bond, where two isotropic orbitals hybridize into the molecular orbital of H2, these flexible groups redistribute upon binding. Via colloidal bond hybridization, isotropic spheres self-assemble into planar monolayers, while anisotropic snowman-like particles self-assemble into hollow monolayer microcapsules. A modest change of the building blocks thus results in a significant leap in the complexity of the self-assembled structures. In other words, these relatively simple building blocks self-assemble into dramatically more complex structures than similar particles that are isotropic or non-deformable

GSK3-mediated raptor phosphorylation supports amino acid-dependent Q2 mTORC1-directed signalling

The mammalian or mechanistic target of rapamycin (mTOR) complex 1 (mTORC1) is a ubiquitously expressed multimeric protein kinase complex that integrates nutrient and growth factor signals for the co-ordinated regulation of cellular metabolism and cell growth. Herein, we demonstrate that suppressing the cellular activity of glycogen synthase kinase-3 (GSK3), by use of pharmacological inhibitors or shRNA-mediated gene silencing, results in substantial reduction in amino acid (AA)-regulated mTORC1-directed signalling, as assessed by phosphorylation of multiple downstream mTORC1 targets. We show that GSK3 regulates mTORC1 activity through its ability to phosphorylate the mTOR-associated scaffold protein raptor (regulatory-associated protein of mTOR) on Ser(859). We further demonstrate that either GSK3 inhibition or expression of a S859A mutated raptor leads to reduced interaction between mTOR and raptor and under these circumstances, irrespective of AA availability, there is a consequential loss in phosphorylation of mTOR substrates, such as p70S6K1 (ribosomal S6 kinase 1) and uncoordinated-51-like kinase (ULK1), which results in increased autophagic flux and reduced cellular proliferation

A network analysis to identify mediators of germline-driven differences in breast cancer prognosis.

Identifying the underlying genetic drivers of the heritability of breast cancer prognosis remains elusive. We adapt a network-based approach to handle underpowered complex datasets to provide new insights into the potential function of germline variants in breast cancer prognosis. This network-based analysis studies ~7.3 million variants in 84,457 breast cancer patients in relation to breast cancer survival and confirms the results on 12,381 independent patients. Aggregating the prognostic effects of genetic variants across multiple genes, we identify four gene modules associated with survival in estrogen receptor (ER)-negative and one in ER-positive disease. The modules show biological enrichment for cancer-related processes such as G-alpha signaling, circadian clock, angiogenesis, and Rho-GTPases in apoptosis

Fine-mapping identifies multiple prostate cancer risk loci at 5p15, one of which associates with TERT expression

Associations between single nucleotide polymorphisms (SNPs) at 5p15 and multiple cancer types have been reported. We have previously shown evidence for a strong association between prostate cancer (PrCa) risk and rs2242652 at 5p15, intronic in the telomerase reverse transcriptase (TERT) gene that encodes TERT. To comprehensively evaluate the association between genetic variation across this region and PrCa, we performed a fine-mapping analysis by genotyping 134 SNPs using a custom Illumina iSelect array or Sequenom MassArray iPlex, followed by imputation of 1094 SNPs in 22 301 PrCa cases and 22 320 controls in The PRACTICAL consortium. Multiple stepwise logistic regression analysis identified four signals in the promoter or intronic regions of TERT that independently associated with PrCa risk. Gene expression analysis of normal prostate tissue showed evidence that SNPs within one of these regions also associated with TERT expression, providing a potential mechanism for predisposition to disease