Factors influencing anion binding stoichiometry : the subtle influence of electronic effects

Six new, charge-neutral norbornene-based receptors 1a,1b– 3a,3b were prepared, and their ability to interact with simple anions in DMSO was investigated using 1H NMR and UV/ Vis spectroscopy. Binding of dihydrogenphosphate by the six receptors appeared to be based solely on steric constraints. In contrast, the binding stoichiometry of 3a and 3b to acetate was controlled by subtle electronic factors.

Student-generated submicro diagrams : a useful tool for teaching and learning chemical equations and stoichiometry

This paper reports on a pedagogical approach to the teaching of chemical equations introduced to first year university students with little previous chemical knowledge. During the instruction period students had to interpret and construct diagrams of reactions at the submicro level, and relate them to chemical equations at the symbolic level with the aim of improving their conceptual understanding of chemical equations and stoichiometry. Students received instruction in symbol conventions, practice through graded tutorial tasks, and feedback on their efforts over the semester. Analysis of the student responses to formative test and summative exam items over consecutive years indicates that there was a consistent improvement in the abilities of the various cohorts to answer stoichiometry questions correctly. The responses provide evidence for diagrams of the submicro level being used as tools for reasoning in solving chemical problems, to recognise misconceptions of chemical formulae and to recognise the value of using various multiple representations of chemical reactions connecting the submicro and symbolic levels of representation. The student-generated submicro diagrams serve as a visualisation tool for teaching and learning abstract concepts in solving stoichiometric problems. We argue that the use of diagrams of the submicro level provides a more complete picture of the reaction, rather than a net summary of a chemical equation, leading to a deeper conceptual understanding.

Stoichiometry of endothermy : shifting the quest from nitrogen to carbon

For many animals, notably herbivores, plants are often an inadequate food source given the low content of protein and high content of C-rich material. This conception is mainly based on studies on ectotherms. The validity of this conception for endotherms is unclear given their much higher carbon requirements for maintenance energy metabolism than ectotherms. Applying stoichiometric principles, we hypothesized that endotherms can cope with diets with much higher (metabolizable) carbon to nitrogen ratios than ectotherms. Using empirical data on birds, eutherian mammals, marsupials and reptiles, we compiled and compared measurements and allometric equations for energy metabolism as well as nitrogen requirements. Our analysis supports our hypothesis that plants, and especially their leaves, are generally sufficiently rich in nitrogen to fulfil protein demands in endotherms, at least during maintenance conditions, but less so in ectotherms. This has important implications with respect to community functioning and the evolution of endothermy.

Combined atom probe tomography and density functional theory investigation of the Al off-stoichiometry of κ-carbides in an austenitic Fe-Mn-Al-C low density steel

We report on the investigation of the off-stoichiometry and site-occupancy of κ-carbide precipitates within an austenitic (γ), Fe-29.8Mn-7.7Al-1.3C (wt.%) alloy using a combination of atom probe tomography and density functional theory. The chemical composition of the κ-carbides as measured by atom probe tomography indicates depletion of both interstitial C and substitutional Al, in comparison to the ideal stoichiometric L′12 bulk perovskite. In this work we demonstrate that both these effects are coupled. The off-stoichiometric concentration of Al can, to a certain extent, be explained by strain caused by the κ/γ mismatch, which facilitates occupation of Al sites in κ-carbide by Mn atoms (MnγAl anti-site defects). The large anti-site concentrations observed by our experiments, however, can only be stabilized if there are C vacancies in the vicinity of the anti-site.

4-Amino-1,8-naphthalimide-based anion receptors: employing the naphthalimide N-H moiety in the cooperative binding of dihydrogenphosphate

The 4-amino-1,8-naphthalimide-based anion receptor 3 binds dihydrogenphosphate with 1:1 stoichiometry through cooperative hydrogen bonding to a naphthalimide N–H and thiourea N–H groups. This was clearly established from ¹H NMR titration experiments in DMSO-d₆ where a substantial shift in the resonance for the naphthalimide N–H was observed concomitant with the expected thiourea N–H chemical shift migration upon successive additions of H₂PO₄⁻. However, whilst ¹H NMR titration experiments indicate that 3 was capable of binding other anions such as acetate, the naphthalimide N–H does not participate and the N–H resonance was essentially invariant during the titration. The lack of cooperative binding in this instance was justifiable on steric grounds.

Fluorescent anion sensors based on 4-amino-1,8-naphthalimide that employ the 4-amino N-H

The new charge neutral 4-amino-1,8-naphthalimide based anion sensors 2 and 3 bind to both acetate and dihydrogenphosphate with 1:1 stoichiometry through hydrogen bonding to both thiourea N–H atoms and in the case of dihydrogenphosphate, the naphthalimide 4 amino N–H group as well. This was clearly established from ¹H NMR titration experiments with H₂PO₄^- in DMSO-d₆ where a substantial shift in the resonance for the naphthalimide N–H was observed concomitant with the expected migration of the thiourea N–H chemical shifts. The binding constants determined from the titration studies indicate that the new sensors bind H₂PO₄^- more strongly than AcO⁻. Fluorescence titrations with sensor 3 indicate quenching of 59% and 36% upon addition of acetate and dihydrogenphosphate, respectively.

Steric and electronic factors influencing recognition by a simple, charge neutral norbornene based anion receptor

Based on 1H NMR studies, subtle electronic factors rather than pre-organisation dictate the binding stoichiometry of the new, norbornene based, anion hosts 1 and 2 with acetate, however, the binding of dihydrogenphosphate appears to be based solely on steric constraints.

Anion recognition and anion-mediated self-assembly with thiourea-functionalised fused [3]polynorbornyl frameworks

Three conformationally preorganised host molecules based on the [3]polynorbornyl framework and incorporating di-urea receptors were synthesised and their interaction with a series of anions investigated by 1H NMR spectroscopy. A high affinity of each host molecule for dihydrogenphosphate (H2PO4–) and dihydrogenpyrophosphate (H2P2O72–) was identified. In addition to binding to the urea receptors of the host molecules, evidence for an interaction involving the non-polar C–H groups within the binding cavity of the framework and guest anions was also discovered. Furthermore, an unusual 2 : 1 host-to-anion stoichiometry was indicated when binding H2P2O72–, and a model for the anion-mediated self-assembly of this complex species is proposed.

Biomimetic processing of nanocrystallite bioactive apatite coating on titanium-zirconium alloy

In this paper nanocrystallite apatite coating on TiZr substrate was prepared by a biomimetic process. Surface morphology, thickness, crystalline phases a~nd bond strength of the coating were investigated by SEM, XRD and tensIle test, respectively. Results show that the apatite coating exhibIts a nanocrystalIite structure with similar stoichiometry to that of natural bone. The apatite layer becomes thicker with the increasing of the SBF immersion time and is firmly adhered to the substrate with the highest average bond strength of 15.5 MPa. This nanocrystallite apatite coating is expected to bond to surrounding bone tissue directly in vivo after implantation.

Photoaffinity labeling of the N-methyltransferase domains of cyclosporin synthetase

The multifunctional polypeptide cyclosporin synthetase (CySyn) remains one of the most complex nonribosomal peptide synthetase described. In this study we used a highly specific photoaffinity labeling procedure with the natural cofactor S-adenosyl-l-methionine (AdoMet), 14C-isotopically labeled at the Sδ methyl group to probe the concerted AdoMet-binding interaction of the N-methyltransferase (N-MTase) centers of CySyn. The binding stoichiometry for the enzyme–AdoMet complex was determined to be 1:7, which is in agreement with inferences made from analysis of the complementary DNA sequence of the simA gene encoding the CySyn polypeptide. The photolabeling of the AdoMet-binding sites displayed homotropic negative cooperativity, characterized by a curvilinear Scatchard plot with upward concavity. Although, the process of N-methyl transfer is not a critical event for peptide elongation, the destabilizing homotropic interactions between N-MTase centers that were observed may represent a mechanism whereby the enzyme preserves the proficiency of the substrate-channeling process of cyclosporin peptide assembly over a broad range of cofactor concentrations. Furthermore, we demonstrated the utility of the photolabeling procedure for tracking the enzyme during purification.

Copper and zinc mediated oligomerisation of Aß peptides

The accumulation of senile plaques composed primarily of aggregated amyloid β-peptide (Aβ), is the major characteristic of Alzheimer’s disease. Many studies correlate plaque accumulation and the presence of metal ions, particularly copper and zinc. The metal binding sites of the amyloid Aβ peptide of Alzheimer’s disease are located in the N-terminal region of the full-length peptide. In this work, the interactions with metals of a model peptide comprising the first 16 amino acid residues of the amyloid Aβ peptide, Aβ(1–16), were studied. The effect of Cu²⁺ and Zn²⁺ binding to Aβ(1–16) on peptide structure and oligomerisation are reported. The results of ESI-MS, gel filtration chromatography and NMR spectroscopy demonstrated formation of oligomeric complexes of the peptide in the presence of the metal ions and revealed the stoichiometry of Cu²⁺ and Zn²⁺ binding to Aβ(1–16), with Cu²⁺ showing a higher affinity for binding the peptide than Zn²⁺.

Mechanochemical synthesis of nanoparticles

The results of recent investigation of the mechanochemical synthesis of inorganic nanoparticles are reviewed. It was demonstrated that, by selecting suitable chemical reaction paths, stoichiometry of starting materials and milling conditions, mechanochemical processing can be used to synthesise a wide range of nanocrystalline particles dispersed within a soluble salt matrix. Selective removal of the matrix phase by washing the resulting powder with appropriate solvents can yield nanoparticles of the desired phase. This technique has been shown to have advantages over other methods of producing nanoparticles in terms of low cost, small particle sizes, low agglomeration, narrow size distributions and uniformity of crystal structure and morphology.

Microstructural development in Al/MgAl2O4 in situ metal matrix composite using value-added silica sources

Al/MgAl2O4 in situ metal matrix composites have been synthesized using value-added silica sources (microsilica and rice husk ash) containing ~97% SiO2 in Al-5 wt.% Mg alloy. The thermodynamics and kinetics of MgAl2O4 formation are discussed in detail. The MgO and MgAl2O4 phases were found to dominate in microsilica (MS) and rice husk ash (RHA) value-added composites, respectively, during the initial stage of holding the composites at 750 °C. A transition phase between MgO and MgAl2O4 was detected by the scanning electron microscopy and energy-dispersive spectroscopy (SEM–EDS) analysis of the particles extracted from the composite using 25% NaOH solution. This confirms that MgO is gradually transformed to MgAl2O4 by the reaction 3SiO2(s)+2MgO(s)+4Al(l)→2MgAl2O4(s)+3Si(l). The stoichiometry of MgAl2O4, n, computed by a new methodology is between 0.79 and 1.18. The reaction between the silica sources and the molten metal stopped after 55% of the silica source was consumed. A gradual increase in mean MgAl2O4 crystallite size, D, from 24 to 36 nm was observed in the samples held for 10 h.

Synthesis of an Al/MgAl2O4 in situ metal matrix composite from silica gel

An aluminum/MgAl2O4 in situ metal matrix composite has been synthesized using silica gel containing B98% SiO2 in an Al–5Mg alloy. The thermodynamics and kinetics of MgAl2O4 formation have been discussed in detail. A transition phase of composition between MgO and MgAl2O4 has been detected in the SEM-EDS analysis of the particles extracted from the composite by a 25% NaOH solution. This confirms the gradual transformation of MgO to MgAl2O4 by the reaction 3SiO2(s)12MgO(s)14Al(l)-2MgAl2O4(s)13Si(l). The stoichiometry, n, of MgAl2O4 has been found to sustain close to 1 and the crystallite growth of MgAl2O4 has been stopped at DB30 nm in the composites held at 7501C up to 10 h.