Functionalized bis(thiosemicarbazonato) complexes of zinc and copper: synthetic platforms toward site-specific radiopharmaceuticals

Two new types of unsymmetrical bis(thiosemicarbazone) proligands and their neutral zinc(II) and copper(II) complexes have been synthesized. These bifunctional ligands both chelate the metal ions and provide pendent amino groups that can be readily functionalized with biologically active molecules. Functionalization has been demonstrated by the synthesis of three water-soluble glucose conjugates of the new zinc(II) bis(thiosemicarbazonato) complexes, and their copper(II) analogues have been prepared in aqueous solution via transmetalation. A range of techniques including NMR, electron paramagnetic resonance, cyclic voltammetry, high-performance liquid chromatography (HPLC), UV/vis, and fluorescence emission spectroscopy have been used to characterize the complexes. Four compounds, including two zinc(II) complexes, have been characterized by X-ray crystallography. The connectivity and conformation of the glucose conjugates have been assigned by NMR spectroscopy. Time-dependent density functional theory calculations have been used to assign the electronic transitions of the copper(II) bis(thiosemicarbazonato) chromophore. Two copper-64-radiolabeled complexes, including one glucose conjugate, have been prepared and characterized using radio-HPLC, and transmetalation is shown to be a viable method for radiolabeling compounds with copper radionuclides. Preliminary cell washout studies have been performed under normoxic conditions, and the uptake and intracellular distribution have been studied using confocal fluorescence microscopy.     

$$\mathbb {Z}_{4}$$-codes and their Gray map images as orthogonal arrays

A classic result of Delsarte connects the strength (as orthogonal array) of a linear code with the minimum weight of its dual: the former is one less than the latter. Since the paper of Hammons et al., there is a lot of interest in codes over rings, especially in codes over \(\mathbb {Z}_{4}\) and their (usually non-linear) binary Gray map images. We show that Delsarte’s observation extends to codes over arbitrary finite commutative rings with identity. Also, we show that the strength of the Gray map image of a \(\mathbb {Z}_{4}\) code is one less than the minimum Lee weight of its Gray map image.     

Non-linear plasmon response to protein binding at a nanostructured gold particle plasmon resonance surface

Rapid adsorption kinetics have been observed for protein binding to a 800 nm aggregated nanoparticle, showing extreme sensitivity resulting from a non-linear particle plasmon response.     

Initiation of the ice phase by marine biogenic surfaces in supersaturated gas and supercooled aqueous phases

Biogenic particles have the potential to affect the formation of ice crystals in the atmosphere with subsequent consequences for the hydrological cycle and climate. We present laboratory observations of heterogeneous ice nucleation in immersion and deposition modes under atmospherically relevant conditions initiated by Nannochloris atomus and Emiliania huxleyi, marine phytoplankton with structurally and chemically distinct cell walls. Temperatures at which freezing, melting, and water uptake occur are observed using optical microscopy. The intact and fragmented unarmoured cells of N. atomus in aqueous NaCl droplets enhance ice nucleation by 10-20 K over the homogeneous freezing limit and can be described by a modified water activity based ice nucleation approach. E. huxleyi cells covered by calcite plates do not enhance droplet freezing temperatures. Both species nucleate ice in the deposition mode at an ice saturation ratio, S(ice), as low as ~1.2 and below 240 K, however, for each, different nucleation modes occur at warmer temperatures. These observations show that markedly different biogenic surfaces have both comparable and contrasting effects on ice nucleation behaviour depending on the presence of the aqueous phase and the extent of supercooling and water vapour supersaturation. We derive heterogeneous ice nucleation rate coefficients, J(het), and cumulative ice nuclei spectra, K, for quantification and analysis using time-dependent and time-independent approaches, respectively. Contact angles, α, derived from J(het)via immersion freezing depend on T, a(w), and S(ice). For deposition freezing, α can be described as a function of S(ice) only. The different approaches yield different predictions of atmospheric ice crystal numbers primarily due to the time evolution allowed for the time-dependent approach with implications for the evolution of mixed-phase and ice clouds.     

High-throughput discovery of novel steric stabilizers for cubic lyotropic liquid crystal nanoparticle dispersions

High-throughput methodologies have been employed to establish structure-property relationships and assess the effectiveness of nonionic steric stabilizers for inverse bicontinuous cubic lyotropic liquid crystalline nanoparticulate dispersions of monoolein and phytantriol. The ability of the stabilizers to disperse the lipids was compared with that of the commonly employed triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymer Pluronic F127, which was used as a positive control. The poly(ethylene oxide) stearate class of stabilizers (commercially known as Myrj) were discovered to be effective as steric stabilizers for cubosomes, while retaining the internal nanostructure of the "parent" bulk phase. In particular, Myrj 59, with an average of 100 poly(ethylene oxide) units, was more effective than F127 at dispersing phytantriol, forming stable phytantriol cubosome dispersions at a concentration of 0.1 wt %, 5-fold lower than that achievable with Pluronic F127. The discovery of this new effective class of stabilizers for cubosomes, specifically enabled by high-throughput approaches, broadens the versatility of components from which to construct these interesting potential drug delivery and medical imaging nanoparticles.     

Neutron bound beta-decay: BOB

Frozen solution samples were made from gold chloride and KAu(CN)₂ solvated with TBP/xylene. The ¹⁹⁷Au M?ssbauer parameters were similar to those same species as frozen solutions or adsorbed onto activated carbon. Solvated samples from EuO dissolved in HCl or H₂SO₄ and frozen gave characteristic Eu(III) spectra. All the spectra were consistent with bonding to the TBP being through hydronium ions or water molecules.     

Sucrose cryo-protection facilitates imaging of whole eye sections by MALDI mass spectrometry

Sucrose is used as a cryo-preservation agent on large mammalian eyes post formalin fixation and is shown to reduce freezing artefacts allowing the collection of 12-μm thick sections from these large aqueous samples. The suitability of this technique for use in MALDI imaging experiments is demonstrated by the acquisition of the first images of lipid distributions within whole sagittal porcine eye sections.     

Opportunities and protocol for the teaching of materials science in africa

During the last 30 years the world's materials around us have changed from ‐ steel, concrete and wood to new materials with their own chemistry, and they constitute a large part of the manufacturing industry and our imports. Emphasis is on polymers, advanced materials for the electronic and medical industries and novel ceramics, amongst others. Yet, a school leaver often doesn't know much, or anything, about steel, concrete or what a plastic bag is and how to recycle it. There is an urgent need to address the improved teaching of materials science, especially in Africa [1, 2]. The NSF in America funded the Materials Science Department at Iowa University to create standards eight, nine and ten, i.e. senior high school, material science course. Sixteen teachers were used to write the notes and teachers manual. We are looking at the use of this course to promote materials science as a third matric science subject. We are of the opinion that this course could do much to improve science teaching in Africa and make the matric student much more conscious of materials around him/her. This presentation (which in some form had been presented at various conferences) mentions what this course in materials science and macromolecules covers and, further what we can do and achieve with multimedia education at university level [3, 4, 5, 6, 7, 8]. It will be based on the courses: MATTER, from Chapman‐Hall, developed by Liverpool University and Macrogalleria, developed by Prof. Lon Mathias at University of Southern Mississippi.