High-frequency nanostructured magnetic materials for integrated inductors

Electroplating is compatible with the deposition of relatively thick layers i.e. several μm to 10s- of μm. However eddy current losses mean that thick layers will have an inferior frequency response. We have used a low content phosphorous bath together with pulse reverse plating to generate Co-rich and Co-deficient multi-nanolayers of CoP having improved saturation magnetisation and a better frequency response. The plating parameters have been optimised in order to produce a material with low loss, and a high permeability of around 700 retained up to 103 MHz for a sample with a thickness of 1.7 μm and a resistivity of 136 μΩ cm.     

Limit theorems for a recursive maximum process with location-dependent periodic intensity-parameter

We investigate the recursive sequence Z _n : =  max {Z _n − 1,λ(Z _n − 1)X _n } where X _n is a sequence of iid random variables with exponential distributions and λ is a periodic positive bounded measurable function. We prove that the Césaro mean of the sequence λ(Z _n ) converges toward the essential minimum of λ. Subsequently we apply this result and obtain a limit theorem for the distributions of the sequence Z _n . The resulting limit is a Gumbel distribution.     

Synthesis and Diels-Alder Reactions of a New Kind of Chiral Dienophiles: Cyclic Vinyl-p-tolylsulfilimines

A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group.     

Vinyl MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

Iterative cross-coupling represents a potentially general approach for the simple, efficient, and flexible construction of natural products, pharmaceuticals, and materials. N-Methyliminodiacetic acid (MIDA) boronates represent a promising platform for the development of this type of synthesis strategy. This report describes the discovery that vinyl MIDA boronate (1) is an air- and chromatographically stable compound that can be conveniently prepared on a multigram scale and serve as a versatile starting material for the preparation of a range of new MIDA boronate building blocks. Analogous to tert-butylethylene, 1 is also an excellent substrate for olefin cross-metathesis, providing access to a range of trans-alkenyl MIDA boronates as single stereoisomers. An improved synthesis of the very versatile bifunctional building block trans-(2-bromovinyl) MIDA boronate (2) is also described. Collectively, these results contribute to the expanding generality of the iterative cross-coupling approach.     

Tuning the Guest‐Binding Ability of a Helically Folded Capsule by In Situ Modification of the Aromatic Oligoamide Backbone

Starting from a previously described aromatic oligoamide helically folded capsule that binds tartaric acid with high affinity and diastereoselectivity, we demonstrate the feasibility of the direct in situ modification of the helix backbone, which results in a conformational change that reduces its affinity for guests by two orders of magnitude. Specifically, ring contraction of the central pyridazine unit into a pyrrole in the full helical sequence was investigated by using electrochemical and chemical processes. The sequence containing the pyrrole was synthesized independently in a convergent manner to ascertain its structure. The conformation of the pyrrolic folded capsule was elucidated in the solid state by X‐ray crystallography and in solution by using ¹H and ¹³C NMR spectroscopy. Solution studies revealed an unanticipated solvent‐dependent equilibrium between the anti–anti and syn–syn conformations of the pyrrole ring with respect to its two adjacent pyridine units. Titrations of the pyrrole‐containing sequence monitored by ¹H NMR spectroscopy confirmed the expected drop in affinity for tartaric acid and malic acid that arises from the conformation change in the backbone that follows the replacement of the pyridazine by a pyrrole. The reduction of the pyridazine to a pyrrole was characterized by cyclic voltammetry both on the entire sequence and on a shorter precursor. The lower cathodic potential of the precursor made its preparative‐scale electroreduction possible. Direct in situ modification of the pyridazine within the entire capsule sequence was achieved chemically by using zinc in acetic acid.     

Increasing the Size of an Aromatic Helical Foldamer Cavity by Strand Intercalation

The postsynthetic modulation of capsules based on helical aromatic oligoamide foldamers would be a powerful approach for controlling their receptor properties without altering the initial monomer sequences. With the goal of developing a method to increase the size of a cavity within a helix, a single‐helical foldamer capsule was synthesized with a wide‐diameter central segment that was designed to intercalate with a second shorter helical strand. Despite the formation of stable double‐helical homodimers (K_dim>10⁷ M ^?1) by the shorter strand, when it was mixed with the single‐helical capsule sequence, a cross‐hybridized double helix was formed with K_a>10⁵ M ^?1. This strategy makes it possible to direct the formation of double‐helical heterodimers. On the basis of solution‐ and solid‐state structural data, this intercalation resulted in an increase in the central‐cavity size to give a new interior volume of approximately 150 ų.     

Characterization of a new epoxy-hydroxycarvotanacetone derivative from the leaf essential oil of Laggera pterodonta from Côte d’Ivoire

The leaf essential oil of Laggera pterodonta (DC.) Sch. Bip. ex Oliv. (Asteraceae) collected in the Eastern Côte d’Ivoire was investigated using a combination of chromatographic (GC-RI, CC, pc-GC) and spectroscopic (GC-MS, ¹³C NMR) techniques. Eighty-three components accounting for 98.0% of the whole composition were identified with 2,5-dimethoxy-p-cymene (43.3%), sabinene (14.1%), α-humulene (9.8%), (E)-β-caryophyllene (7.2%) and germacrene D (5.2%) as major compounds. This study led to the structural elucidation of a new natural compound, (3αH,4βH,6αH,1αMe)-1,6-epoxy-3-hydroxycarvotanacetone, angelic acid ester from the leaf oil by 1D and 2D NMR spectroscopy.