Reaction of [18F]Fluoride at Heteroatoms and Metals for Imaging of Peptides and Proteins by Positron Emission Tomography

The ability to radiolabel proteins with [18F]fluoride enables the use of positron emission tomography (PET) for the early detection, staging and diagnosis of disease. The direct fluorination of native proteins through C-F bond formation is, however, a difficult task. The aqueous environments required by proteins severely hampers fluorination yields while the dry, organic solvents that promote nucleophilic fluorination can denature proteins. To circumvent these issues, indirect fluorination methods making use of prosthetic groups that are first fluorinated and then conjugated to a protein have become commonplace. But, when it comes to the radiofluorination of proteins, these indirect methods are not always suited to the short half-life of the fluorine-18 radionuclide (110 min). This review explores radiofluorination through bond formation with fluoride at boron, metal complexes, silicon, phosphorus and sulfur. The potential for these techniques to be used for the direct, aqueous radiolabeling of proteins with [18F]fluoride is discussed

Optimal Fluctuations and Tail States of non-Hermitian Operators

We develop a general variational approach to study the statistical properties of the tail states of a wide class of non-Hermitian operators. The utility of the method, which is a refinement of the instanton approach introduced by Zittartz and Langer, is illustrated in detail by reference to the problem of a quantum particle propagating in an imaginary scalar potential.Comment: 4 pages, 2 figures, to appear in PR

Path Integral Approach to the Scattering Theory of Quantum Transport

The scattering theory of quantum transport relates transport properties of disordered mesoscopic conductors to their transfer matrix \bbox{T}. We introduce a novel approach to the statistics of transport quantities which expresses the probability distribution of \bbox{T} as a path integral. The path integal is derived for a model of conductors with broken time reversal invariance in arbitrary dimensions. It is applied to the Dorokhov-Mello-Pereyra-Kumar (DMPK) equation which describes quasi-one-dimensional wires. We use the equivalent channel model whose probability distribution for the eigenvalues of \bbox{TT}^{\dagger} is equivalent to the DMPK equation independent of the values of the forward scattering mean free paths. We find that infinitely strong forward scattering corresponds to diffusion on the coset space of the transfer matrix group. It is shown that the saddle point of the path integral corresponds to ballistic conductors with large conductances. We solve the saddle point equation and recover random matrix theory from the saddle point approximation to the path integral.Comment: REVTEX, 9 pages, no figure

Sub-micron moulding topological mass transport regimes in angled vortex fluidic flow

Shear stress in dynamic thin films, as in vortex fluidics, can be harnessed for generating non-equilibrium conditions, but the nature of the fluid flow is not understood. A rapidly rotating inclined tube in the vortex fluidic device (VFD) imparts shear stress (mechanical energy) into a thin film of liquid, depending on the physical characteristics of the liquid and rotational speed,ω, tilt angle,θ, and diameter of the tube. Through understanding that the fluid exhibits resonance behaviours from the confining boundaries of the glass surface and the meniscus that determines the liquid film thickness, we have established specific topological mass transport regimes. These topologies have been established through materials processing, as spinning top flow normal to the surface of the tube, double-helical flow across the thin film, and spicular flow, a transitional region where both effects contribute. The manifestation of mass transport patterns within the film have been observed by monitoring the mixing time, temperature profile, and film thickness against increasing rotational speed,ω. In addition, these flow patterns have unique signatures that enable the morphology of nanomaterials processed in the VFD to be predicted, for example in reversible scrolling and crumbling graphene oxide sheets. Shear-stress induced recrystallisation, crystallisation and polymerisation, at different rotational speeds, provide moulds of high-shear topologies, as ‘positive’ and ‘negative’ spicular flow behaviour. ‘Molecular drilling’ of holes in a thin film of polysulfone demonstrate spatial arrangement of double-helices. The grand sum of the different behavioural regimes is a general fluid flow model that accounts for all processing in the VFD at an optimal tilt angle of 45°, and provides a new concept in the fabrication of novel nanomaterials and controlling the organisation of matter

Crosslinker Copolymerization for Property Control in Inverse Vulcanization.

Sulfur is an underused by-product of the petrochemicals industry. Recent research into inverse vulcanization has shown how this excess sulfur can be transformed into functional polymers, by stabilization with organic crosslinkers. For these interesting new materials to realize their potential for applications, more understanding and control of their physical properties is needed. Here we report four new terpolymers prepared from sulfur and two distinct alkene monomers that can be predictively tuned in glass transition, molecular weight, solubility, mechanical properties, and color

Norbornene probes for the study of cysteine oxidation

© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license http://creativecommons.org/licenses/by/4.0/).Cysteine residues on proteins can react with cellular oxidants such as hydrogen peroxide. While this process is important for scavenging excess reactive oxygen species, the products of this oxidation may also mediate cell signalling. To understand the role of cysteine oxidation in biology, selective probes are required to detect and quantify its occurrence. Cysteine oxidation products such as sulfenic acids are sometimes unstable and therefore short-lived. If such cysteine derivatives are to be analysed, rapid reaction with the probe is required. Here we introduce norbornene derivatives as probes for cysteine oxidation, and demonstrate their ability to trap sulfenic acids. The synthesis of norbornene derivatives containing alkyne or biotin affinity tags are also reported to facilitate the use of these probes in chemical biology and proteomics