(CYCLOPENTADIENONE)IRON COMPLEXES IN REACTIONS INVOLVING HYDROGEN TRANSFER

The PhD project focused on the synthesis and catalytic applications of (cyclopentadienone)iron complexes in reactions involving hydrogen transfer. The manuscript is divided into five chapters, and after a rather comprehensive review on the state of the art in chapter 1, the thesis describes, in the remaining four chapters, the original achievements of the PhD candidate. In particular, chapter 2 describes the applications of highly active [bis(hexamethylene)cyclopentadienone]iron tricarbonyl pre-catalyst for the reduction of imine bonds under transfer hydrogenation conditions and for the reductive amination of carbonyl compounds. In chapter 3, the application of the above mentioned pre-catalyst to alcohol amination reactions via a hydrogen borrowing mechanism is discussed. Chapter 4 deals with enantioselective ketone hydrogenations using chiral (cyclopentadienone)iron complexes containing a stereogenic plane (prepared in racemic form and resolved by chiral HPLC), and with the synthesis of chiral macrocyclic (cyclopentadienone)iron complexes, putatively more suited for the transfer of the chiral information from the catalyst to the substrate. Finally, Chapter 5 describes the immobilization of (cyclopentadienone)iron complexes into a solid support, namely Metal Organic Frameworks (MOFs), to realize an active heterogeneous (cyclopentadienone)iron catalyst for catalyst recycling in batch hydrogenation reactions and potential applications in flow processes

Asymptotic properties of eigenmatrices of a large sample covariance matrix

Let $S_n=\frac{1}{n}X_nX_n^*$ where $X_n=\{X_{ij}\}$ is a $p\times n$ matrix with i.i.d. complex standardized entries having finite fourth moments. Let $Y_n(\mathbf {t}_1,\mathbf {t}_2,\sigma)=\sqrt{p}({\mathbf {x}}_n(\mathbf {t}_1)^*(S_n+\sigma I)^{-1}{\mathbf {x}}_n(\mathbf {t}_2)-{\mathbf {x}}_n(\mathbf {t}_1)^*{\mathbf {x}}_n(\mathbf {t}_2)m_n(\sigma))$ in which $\sigma>0$ and $m_n(\sigma)=\int\frac{dF_{y_n}(x)}{x+\sigma}$ where $F_{y_n}(x)$ is the Mar\v{c}enko--Pastur law with parameter $y_n=p/n$; which converges to a positive constant as $n\to\infty$, and ${\mathbf {x}}_n(\mathbf {t}_1)$ and ${\mathbf {x}}_n(\mathbf {t}_2)$ are unit vectors in ${\Bbb{C}}^p$, having indices $\mathbf {t}_1$ and $\mathbf {t}_2$, ranging in a compact subset of a finite-dimensional Euclidean space. In this paper, we prove that the sequence $Y_n(\mathbf {t}_1,\mathbf {t}_2,\sigma)$ converges weakly to a $(2m+1)$-dimensional Gaussian process. This result provides further evidence in support of the conjecture that the distribution of the eigenmatrix of $S_n$ is asymptotically close to that of a Haar-distributed unitary matrix.Comment: Published in at http://dx.doi.org/10.1214/10-AAP748 the Annals of Applied Probability (http://www.imstat.org/aap/) by the Institute of Mathematical Statistics (http://www.imstat.org

Impurity scattering and Friedel oscillations in mono-layer black phosphorus

We study the effect of impurity scattering effect in black phosphorurene (BP) in this work. For single impurity, we calculate impurity induced local density of states (LDOS) in momentum space numerically based on tight-binding Hamiltonian. In real space, we calculate LDOS and Friedel oscillation analytically. LDOS shows strong anisotropy in BP. Many impurities in BP are investigated using $T$-matrix approximation when the density is low. Midgap states appear in band gap with peaks in DOS. The peaks of midgap states are dependent on impurity potential. For finite positive potential, the impurity tends to bind negative charge carriers and vise versa. The infinite impurity potential problem is related to chiral symmetry in BP

Heterodimerization of apelin receptor and neurotensin receptor 1 induces phosphorylation of ERK1/2 and cell proliferation via Gαq-mediated mechanism

Dimerization of G protein-coupled receptors (GPCRs) is crucial for receptor function including agonist affinity, efficacy, trafficking and specificity of signal transduction, including G protein coupling. Emerging data suggest that the cardiovascular system is the main target of apelin, which exerts an overall neuroprotective role, and is a positive regulator of angiotensin-converting enzyme 2 (ACE2) in heart failure. Moreover, ACE2 cleaves off C-terminal residues of vasoactive peptides including apelin-13, and neurotensin that activate the apelin receptor (APJ) and neurotensin receptor 1 (NTSR1) respectively, that belong to the A class of GPCRs. Therefore, based on the similar mode of modification by ACE2 at peptide level, the homology at amino acid level and the capability of forming dimers with other GPCRs, we have been suggested that APJ and NTSR1 can form a functional heterodimer. Using co-immunoprecipitation, BRET and FRET, we provided conclusive evidence of heterodimerization between APJ and NTSR1 in a constitutive and induced form. Upon agonist stimulation, hetrodimerization enhanced ERK1/2 activation and increased proliferation via activation of Gq α-subunits. These novel data provide evidence for a physiological role of APJ/NTSR1 heterodimers in terms of ERK1/2 activation and increased intracellular calcium and induced cell proliferation and provide potential new pharmaceutical targets for cardiovascular disease. © 2014 The Authors

Tick-borne encephalitis virus induces chemokine RANTES expression via activation of IRF-3 pathway.

BACKGROUND: Tick-borne encephalitis virus (TBEV) is one of the most important flaviviruses that targets the central nervous system (CNS) and causes encephalitides in humans. Although neuroinflammatory mechanisms may contribute to brain tissue destruction, the induction pathways and potential roles of specific chemokines in TBEV-mediated neurological disease are poorly understood. METHODS: BALB/c mice were intracerebrally injected with TBEV, followed by evaluation of chemokine and cytokine profiles using protein array analysis. The virus-infected mice were treated with the CC chemokine antagonist Met-RANTES or anti-RANTES mAb to determine the role of RANTES in affecting TBEV-induced neurological disease. The underlying signaling mechanisms were delineated using RANTES promoter luciferase reporter assay, siRNA-mediated knockdown, and pharmacological inhibitors in human brain-derived cell culture models. RESULTS: In a mouse model, pathological features including marked inflammatory cell infiltrates were observed in brain sections, which correlated with a robust up-regulation of RANTES within the brain but not in peripheral tissues and sera. Antagonizing RANTES within CNS extended the survival of mice and reduced accumulation of infiltrating cells in the brain after TBEV infection. Through in vitro studies, we show that virus infection up-regulated RANTES production at both mRNA and protein levels in human brain-derived cell lines and primary progenitor-derived astrocytes. Furthermore, IRF-3 pathway appeared to be essential for TBEV-induced RANTES production. Site mutation of an IRF-3-binding motif abrogated the RANTES promoter activity in virus-infected brain cells. Moreover, IRF-3 was activated upon TBEV infection as evidenced by phosphorylation of TBK1 and IRF-3, while blockade of IRF-3 activation drastically reduced virus-induced RANTES expression. CONCLUSIONS: Our findings together provide insights into the molecular mechanism underlying RANTES production induced by TBEV, highlighting its potential importance in the process of neuroinflammatory responses to TBEV infection

Sizing energy storage on the 11kV distribution network

The cost and limited flexibility of traditional approaches to 11kV network reinforcement threatens to constrain the uptake of low carbon technologies. Ofgem has released £500m of funding for DNOs to trial innovative techniques and share the learning with the rest of the industry. One of the techniques under study is the addition of Energy Storage at key substations to the network to help with peak load lopping. This paper looks in detail at the sizing algorithm for use in the assessment of alternatives to traditional reinforcement and investigates a method of sizing a battery for use on a Network taking into account load growth, capacity fade and battery lifecycle issues. A further complication to the analysis is the method of operation of the battery system and how this affects the Depth of Discharge (DoD). The proposed method is being trialled on an area of 11kV network in Milton Keynes Central area and the simulation results are presented in this paper

Fiber Based Multiple-Access Optical Frequency Dissemination

We demonstrate a fiber based multiple-access optical frequency dissemination scheme. Without using any additional laser sources, we reproduce the stable disseminated frequency at an arbitrary point of fiber link. Relative frequency stability of 3E10^{-16}/s and 4E10^{-18}/10^4s is obtained. A branching fiber network for highly-precision synchronization of optical frequency is made possible by this method and its applications are discussed.Comment: 5 pages, 3 figure