Structure and optical properties of Zn_xCd_1-xS and Cu:Zn_xCd_1-xS templated on DNA molecules

\ua9 2024 The Author(s). Published by IOP Publishing Ltd.One-dimensional ZnxCd1−xS and Cu: Znx Cd1−x S nanostructures were prepared using DNA as a template to promote growth along the molecular axis. The formation of homogeneously alloyed nanocrystals with cubic zinc blende-type structures was verified using x-ray diffraction and Raman spectroscopy. X-ray photoemission spectra revealed the presence of Cu(I) in the doped Cu: Znx Cd1−x S nanocrystals. The effectiveness of the DNA template to direct the semiconductor growth in one dimension was demonstrated by AFM and TEM. The nanostructures displayed a granular morphology comprising nanoparticles with an average diameter of 14 nm composed of assemblies of smaller crystallites of 2.0 nm in size. Rope-like assemblies with an average diameter of 48 nm and extending in length to several hundred micrometres were obtained by evaporation-induced self-assembly. UV-Vis absorption and emission spectra indicated that the optical bandgaps (2.89-4.00eV) and photoluminescence peaks (608-819 nm) of the DNA-templated nanocrystals could be precisely controlled by modifying the molar ratios of their Zn/Cd precursors. Doping with Cu(I) gave an increase in photoluminescence intensity and a composition-independent red-shift of 0.23 eV. The preparation of DNA-templated Znx Cd1−x S and Cu: Znx Cd1−x S provides a simple, low-temperature route to aqueous dispersions of inorganic materials with controlled optical gap

Diffusion Models of Mass Transport for the Characterisation of Amperometric Gas Sensors

\ua9 2024 The Authors. ChemElectroChem published by Wiley-VCH GmbH. A diffusion model for the analysis of chronoamperometric data in response to a concentration step is developed for amperometric gas sensors. This analysis avoids the difficulties with standard potentiodynamic measurements at the large specific area, high capacitance electrodes employed in these sensors. Despite the fact that typical devices comprise multiple layers with varying thicknesses and diffusivities, we show that typical chronoamperometric traces can be fitted to a simple diffusion model with a single parameter (Formula presented.) where L is an overall effective thickness of the diffusion barrier and D is an effective diffusion coefficient. Through a comparison of the transient and steady-state current, independent estimates of L and D in the devices can be made. The model is also extended to cover cases with interfacial kinetic barriers; such kinetic limitations lead to a change in the effective values L and D, but the simple diffusion model remains a good fit to the data. This analysis shows that transient sensor responses can be characterised by a single parameter τ and conversely that deviations from this regression model cannot be assigned to (i) complex layer architectures or (ii) interlayer kinetic barriers. Instead, we show that non-uniform accessibility effects arising from a distribution of diffusion rates across the device lead to deviations from the simple regression model, but that they may be captured approximately by a more complex model in which τ has a probability distribution

Enhancing the kinetics of hydrazone exchange processes: an experimental and computational study

The capacity of hydrazone bonds to readily undergo component exchange processes sees their extensive utilization in dynamic combinatorial chemistry. The kinetics of hydrazone exchange are optimal at pH ∼4.5, which limits the use of hydrazone-based dynamic combinatorial libraries, particularly for biological targets which are only stable at near-neutral pH values. It would thus be advantageous if hydrazone exchange proceeded with faster rates at pH values closer to neutral. We experimentally and computationally evaluated the hypothesis that hydrazones possessing neighbouring acidic or basic functional groups within the carbonyl-derived moitety of the hydrazone would enhance exchange rates. Our work suggests that judiciously placed N- or O-hydrogen bond acceptors within the carbonyl-derived moiety of the hydrazone stabilize transition states via hydrogen bonding interactions, providing a valuable boost to exchange kinetics at near-neutral pH values. We anticipate these findings will be of interest in dynamic combinatorial chemistry, dynamic covalent polymers/materials, functionalized nanoparticles and interlocked molecules, all of which may benefit from hydrazone exchange processes able to operate at near-neutral pH values

Templating Iron(III) Oxides on DNA Molecules

\ua9 2024 by the authors. Fe(III) oxides were prepared as free nanoparticles and on DNA templates via the precipitation of Fe(III) salts with NaOH in the presence/absence of DNA. Through control of the pH and temperature, FeOOH and Fe2O3 were synthesised. The formation of templated materials FeOOH/DNA and Fe2O3/DNA was confirmed using UV-Vis absorption and FTIR spectra. The direct optical gap of Fe2O3/DNA was estimated as 3.2 eV; the absorption by FeOOH/DNA and Fe2O3/DNA at longer wavelengths is weaker, but consistent with indirect gaps near 2 eV. X-ray photoelectron spectra confirmed the presence of Fe(III) and DNA in the templated samples. Analysis of the X-ray diffraction patterns of both templated and non-templated FeOOH and Fe2O3 demonstrated that the materials were the α-FeOOH and α-Fe2O3 polymorphs with crystallite diameters of the DNA-templated materials estimated as 7.6 nm and 6.8 nm. Transmission electron microscopy showed needle-like crystals of both FeOOH and Fe2O3, but the Fe2O3 contains some globular structures. In contrast, the morphology of FeOOH/DNA and Fe2O3/DNA consists of needle-like crystallites of the respective oxides organised into complex dendritic structures with a length on the 10 μm scale formed by the DNA molecules. Finally, scanned conductance microscopy provided evidence for the conductivity of the FeOOH/DNA after alignment via molecular combing on an Si/SiO2 substrate. Fe2O3/DNA did not exhibit any detectable conductivity

Comparative Transcriptional and Genomic Analysis of Plasmodium falciparum Field Isolates

Mechanisms for differential regulation of gene expression may underlie much of the phenotypic variation and adaptability of malaria parasites. Here we describe transcriptional variation among culture-adapted field isolates of Plasmodium falciparum, the species responsible for most malarial disease. It was found that genes coding for parasite protein export into the red cell cytosol and onto its surface, and genes coding for sexual stage proteins involved in parasite transmission are up-regulated in field isolates compared with long-term laboratory isolates. Much of this variability was associated with the loss of small or large chromosomal segments, or other forms of gene copy number variation that are prevalent in the P. falciparum genome (copy number variants, CNVs). Expression levels of genes inside these segments were correlated to that of genes outside and adjacent to the segment boundaries, and this association declined with distance from the CNV boundary. This observation could not be explained by copy number variation in these adjacent genes. This suggests a local-acting regulatory role for CNVs in transcription of neighboring genes and helps explain the chromosomal clustering that we observed here. Transcriptional co-regulation of physical clusters of adaptive genes may provide a way for the parasite to readily adapt to its highly heterogeneous and strongly selective environment

Ontology-based end-user visual query formulation: Why, what, who, how, and which?

Value creation in an organisation is a time-sensitive and data-intensive process, yet it is often delayed and bounded by the reliance on IT experts extracting data for domain experts. Hence, there is a need for providing people who are not professional developers with the flexibility to pose relatively complex and ad hoc queries in an easy and intuitive way. In this respect, visual methods for query formulation undertake the challenge of making querying independent of users’ technical skills and the knowledge of the underlying textual query language and the structure of data. An ontology is more promising than the logical schema of the underlying data for guiding users in formulating queries, since it provides a richer vocabulary closer to the users’ understanding. However, on the one hand, today the most of world’s enterprise data reside in relational databases rather than triple stores, and on the other, visual query formulation has become more compelling due to ever-increasing data size and complexity—known as Big Data. This article presents and argues for ontology-based visual query formulation for end-users; discusses its feasibility in terms of ontology-based data access, which virtualises legacy relational databases as RDF, and the dimensions of Big Data; presents key conceptual aspects and dimensions, challenges, and requirements; and reviews, categorises, and discusses notable approaches and systems