Hydrogen bonding control of molecular self-assembly

In this short review we describe approaches to the design and construction of synthetic molecules that mimic the process of self organization that is at the heart of biological complexity. Multi-subunit enzymes, viruses, and higher order DNA structures are formed by the non-covalent association of many smaller components. This self-assembly is controlled by the nature, number and orientation of interacting groups on the surface of the subunits. The central problem lies in overcoming the unfavorable entropy of multi-subunit association by significant enthalpic contribution from the binding of complementary regions on the subunits. We will place particular emphasis on the design of synthetic molecules that use hydrogen bonding interactions to control the formation of aggregates of well-defined structure.     

SERS‐based detection of barcoded gold nanoparticle assemblies from within animal tissue

We have explored the potential of deep Raman spectroscopy, specifically surface‐enhanced spatially offset Raman spectroscopy (SESORS), for non‐invasive detection from within animal tissue, by employing SERS‐barcoded nanoparticle (NP) assemblies as the diagnostic agent. This concept has been experimentally verified in a clinically‐relevant backscattered Raman system with an excitation line of 785 nm under ex vivo conditions. We have shown that our SORS system, with a fixed offset of 2–3 mm, offered sensitive probing of injected 2‐quinolinethiol‐barcoded NP assemblies through animal tissue containing both protein and lipid. In comparison with that of non‐aggregated SERS‐barcoded gold NPs, we have demonstrated that the tailored SERS‐barcoded aggregated NP assemblies have significantly higher detection sensitivity. We report that these NP assemblies can be readily detected at depths of 7–8 mm from within animal proteinaceous tissue with high signal‐to‐noise ratio. In addition, they could also be detected from beneath 1–2 mm of animal tissue with high lipid content, which generally poses a challenge because of high absorption of lipids in the near‐infrared region. We have also shown that the signal intensity and signal‐to‐noise ratio at a particular depth is a function of the SERS tag concentration used and that our SORS system has a 2‐quinolinethiol detection limit of 10⁻⁶ M. Higher detection depths may possibly be obtained with optimization of the NP assemblies, along with improvements in the instrumentation. Such NP assemblies offer prospects for in vivo, non‐invasive detection of tumours along with scope for incorporation of drugs and their targeted and controlled release at tumour sites. These diagnostic agents combined with drug delivery systems could serve as a ‘theranostic agent’, an integration of diagnostics and therapeutics into a single platform. Copyright © 2013 John Wiley & Sons, Ltd.     

Implementing inquiry-oriented curriculum: From the mathematicians’ perspective

As part of an effort to scale up an instructional innovation in abstract algebra, several mathematicians have implemented an inquiry-oriented, group theory curriculum. Three of those mathematicians (co-authors here) also participated in iterative rounds of interviews designed to document and investigate their experiences as they worked to implement this curriculum. Analyses of these interviews uncovered three themes that were important to these mathematicians: coverage, goals for student learning, and the role of the teacher. Here, by drawing on interview data, classroom data, and first person commentaries, we will present and discuss each teacher's perspective on these three themes.     

Vibrational spectroscopic study of the contents of a chest excavated from the wreck of the HMS Pandora

The FT-IR and Raman spectroscopic analysis of a red powder found in a chest from an officer's cabin during the excavation of the wreck of the 18th Century frigate HMS Pandora have confirmed that the pigment is cinnabar, mercury(II) sulphide. Weaker signals in the Raman spectrum are assignable to a proteinaceous material, such as collagen, typical of a degraded vellum or parchment. Comparison of the Raman spectra with that of a pigmented seal from a 1786 Lieutenant's commission demonstrated that the beeswax component of the seal was not observable.     

Isomorphous replacement in nylon 6 by 4-aminomethylcyclohexanecarboxylic acid

It was desired to determine the effect of geometric configuration on the ability of 4-aminomethylcyclohexanecarboxylic acid (AMCC) to “isomorphously” replace ε-aminocaproic acid residues in nylon 6. However, we found that cis-AMCC isomerized to the more thermodynamically stable trans isomer during copolymerization with caprolactam (CL) and also during homopolymerization. A 20/80 cis/trans ratio of AMCC residues was found in the 50:50 copolyamides regardless of whether a high-cis (72/28) or high-trans (15/85) AMCC was used. Powder x-ray diagrams showed similar interplanar spacings for the copolyamides made from both high-cis and high-trans AMCC. The x-ray study also showed that the nylon 6 lattice can accommodate less than 30 mole-% AMCC residues before a new structure appears. DTA and TGA data of the CL:AMCC copolyamide showed that AMCC raised the melting point, T_g, T_c, and stability of nylon 6.     

Synthesis of substituted terpyridine ligands for use in protein purification

A number of 4,4″-disubstituted terpyridines bearing a 4′-thioethanamine linker, and regioisomers thereof, have been synthesised from 4-substituted picolinates. The substituted terpyridines were immobilised onto epoxy-activated Sepharose™ FF gel, creating functionalised solid supports for the fractionation of proteins—including antibodies—by mixed mode affinity chromatography. The metal chelating properties of the immobilised ligand render the stationary phase also amenable for use in immobilised metal-ion affinity chromatography (IMAC), and have been demonstrated with the purification of suitably tagged green fluorescent protein (GFP).     

Phenomenological theory of the increase in the superconducting transition temperature in thin film layered sandwiches

A phenomenological theory is presented to account for the observed increase in the critical temperature, as a function of the number of layers, of multilayer sandwiches composed of alternating superconducting and insulating layers. The transition temperature of the layered compound NbSe₂ when cleaved down to a small number of layers and the pressure dependence of the transition temperature of bulk NbSe₂ can also be fitted into this scheme.