Compositional variations in monomeric trimethylsilylated allyl lanthanide complexes

Treatment of three equivalents of the potassium salt of the bis(1,3-trimethylsilyl)allyl anion with various late lanthanide triflates (M = Dy, Ho, Er, Tm, Lu) produces the unsolvated triallyllanthanide complexes (A′ = 1,3-(SiMe₃)₂C₃H₃). The use of lanthanide halides (Cl, I) with the potassium allyl also generates neutral complexes, but when lanthanide iodides and the corresponding lithium allyl are combined, the lanthanate species are formed. Trends in the bonding of lanthanide allyl complexes with the trimethylsilylated-allyl ligand are explored and compared with those of cyclopentadienyl lanthanide complexes.     

Brazilian <Emphasis Type="Italic">Dioscoreaceas</Emphasis> starches

Determination of the characteristics of native starches is crucial in order to select their best application in various industrial fields. Thus, two different types of non-traditional native starches from the Dioscoreaceas species (Dioscorea sp. and Dioscorea piperifolia Humb. var. Wild) were studied regarding their thermal, structural and rheological properties. The results were contrasted with traditional commercial starch sources (potato, cassava and corn). From the thermogravimetric results (TG/DTG), D. piperifolia starch obtained the highest thermal stability of the samples, except for potato starch. Furthermore, using differential scanning calorimetry and viscoamylograph profiles (RVA), it was found that the Dioscoreaceas starches presented a higher onset (T _o) temperature and susceptibility to retrogradation. They also showed lower values in relation to relative crystallinity, which was calculated from their X-ray patterns and tendency to white (L*) colour. The shapes of the Discoreaceas starch granules were determined using electron microscopy; it was found that as the potato starch the Dioscoreaceas starches showed a wide range of particle size.     

Exploring the Role of Surface States in Emissive Carbon Nanodots: Analysis at Single-Particle Level

Fluorescent carbon nanodots (CDs) have been highlighted as promising semiconducting materials due to their outstanding chemical and optical properties. However, the intrinsic heterogeneity of CDs has impeded a clear understanding of the mechanisms behind their photophysical properties. In this study, as-prepared CDs are fractionated via chromatography to reduce their structural and chemical heterogeneity and analyzed through ensemble and single-particle spectroscopies. Many single particles reveal fluorescence intensity fluctuations between two or more discrete levels with bi-exponential decays. While the intrinsic τ₁ components are uniform among single particles, the τ₂ components from molecule-like emissions spans a wider range of lifetimes, reflecting the inhomogeneity of the surface states. Furthermore, it is concluded that the relative population and chemical states of surface functional groups in CDs have a significant impact on emissive states, brightness, blinking, stability, and lifetime distribution of photoluminescence.     

Two-Way Tables: Issues at the Heart of Statistics and Probability for Students and Teachers

Some problems exist at the intersection of statistics and probability, creating a dilemma in relation to the best approach to assist student understanding. Such is the case with problems presented in two-way tables representing conditional information. The difficulty can be confounded if the context within which the problem is set is one where students have preconceived opinions on the direction of the potential association present. This article considers school students’ responses to two problems of association, with data presented in 2 × 2 tables. A hierarchical rubric is presented to document students’ understandings. Teachers’ pedagogical content knowledge is also considered in relation to the same two problems. Findings include a surprising relationship of outcomes for students across the problem contexts and some concern about teachers’ pedagogical content knowledge in this area of the curriculum.     

Evaluation of Chebyshev pseudospectral methods for third order differential equations

When the standard Chebyshev collocation method is used to solve a third order differential equation with one Neumann boundary condition and two Dirichlet boundary conditions, the resulting differentiation matrix has spurious positive eigenvalues and extreme eigenvalue already reaching O(N ⁵ for N = 64. Stable time-steps are therefore very small in this case. A matrix operator with better stability properties is obtained by using the modified Chebyshev collocation method, introduced by Kosloff and Tal Ezer [3]. By a correct choice of mapping and implementation of the Neumann boundary condition, the matrix operator has extreme eigenvalue less than O(N ⁴. The pseudospectral and modified pseudospectral methods are implemented for the solution of one-dimensional third-order partial differential equations and the accuracy of the solutions compared with those by finite difference techniques. The comparison verifies the stability analysis and the modified method allows larger time-steps. Moreover, to obtain the accuracy of the pseudospectral method the finite difference methods are substantially more expensive. Also, for the small N tested, N ⩽ 16, the modified pseudospectral method cannot compete with the standard approach. This revised version was published online in August 2006 with corrections to the Cover Date.     

Introducing variable cell shape methods in field theory simulations of polymers

We propose a new method for carrying out field-theoretic simulations of polymer systems under conditions of prescribed external stress, allowing for shape changes in the simulation box. A compact expression for the deviatoric stress tensor is derived in terms of the chain propagator, and it is used to monitor changes in the box shape according to a simple relaxation scheme. The method allows fully relaxed, stress free configurations to be obtained even in nontrivial morphologies, and it enables the study of morphology transitions induced by external stresses.     

Calculation of the streaming potential near a rotating disk

A corrected theory of the streaming potential in the vicinity of a disk-shaped sample rotating in an electrolytic solution is presented. When streaming-potential measurements on a variety of materials were reduced to a zeta potential according to a prior theory, the results exceeded expected values by a factor of approximately 2, even though other aspects of the same experiments seemed to confirm the theory. Investigation of the source of the discrepancy revealed a flaw in the prior theory. The crucial understanding is that the surface current produced by the rotation of the disk emerges from the diffuse layer and enters the bulk solution at the periphery of the disk. The new treatment accounts entirely for the discrepancy between literature data and results based on the prior theory.     

Amphipathic helices as mediators of the membrane interaction of amphitropic proteins, and as modulators of bilayer physical properties

The amphipathic helix (AH) motif is used by a subset of amphitropic proteins to accomplish reversible and controlled association with the interfacial zone of membranes. Functioning as more than mere membrane anchoring domains, amphipathic helices can serve as autoinhibitory domains to suppress the protein activity in its soluble form, and as sensors or modulators of membrane curvature. Thus amphipathic helices can both respond to and modulate membrane physical properties. These and other features are illustrated by the behavior of CTP: phosphocholine cytidylyltransferase (CCT), a key regulatory enzyme in PC synthesis. A comparison of the physico-chemical features of CCT's AH motif and 10 others reveals similarities and several differences. The importance of these parameters to the particulars of the membrane interaction and to functional consequences requires more systematic exploration. The membrane partitioning of amphitropic proteins with AH motifs can be regulated by various strategies including changes in membrane lipid composition, phosphorylation, ligand-induced conformational changes, and membrane curvature. Several amphitropic proteins that control budding or tubule formation in cells have AH motifs. The insertion of the hydrophobic face of these amphipathic helices generates an asymmetry in the lateral pressure of the two leaflets resulting in an induction of positive curvature. Curvature induction or stabilization may be a universal property of AHA proteins, not just those involved in budding, but this possibility requires further demonstration.     

Concise,efficient and highly selective asymmetric synthesis of (+)-(3S,4R)-cisapride

A concise asymmetric synthesis of the gastroprokinetic agent (+)-(3S,4R)-cisapride {(+)-(3S,4R)-N(1)-[3′-(4″-fluorophenoxy)propyl]-3-methoxy-4-(2″′-methoxy-4″′-amino-5″′-chlorobenzamido)piperidine} from commercially available starting materials has been developed. The key step of this synthesis employs the diastereoselective conjugate addition of lithium (R)-N-benzyl-N-(α-methylbenzyl)amide to tert-butyl 5-[N-3′-(4″-fluorophenoxy)propyl-N-allylamino]pent-2-enoate and in situ enolate oxidation with (?)-camphorsulfonyloxaziridine to set the (3S,4R)-configuration found within the piperidine ring of the product. This synthesis proceeds in 9 steps from commercially available 1-(4′-fluorophenoxy)-3-bromopropane with an overall yield of 19%.