Extending distannoxane double ladders using rigid spacers: a double ladder with eight chiral tin atoms-and a twist!

The new bulky silicon-containing ditin precursor p-(RCl₂SnCH₂SiMe₂)₂C₆H₄ (R = CH₂SiMe₃ (4)) has been synthesized and further reacted to form a unique double ladder {[p-(R(Cl)SnCH₂SiMe₂)₂C₆H₄]O}₄ (6). The two layers within 6 are twisted with respect to one another, resulting in a helical motif and a total absence of molecular symmetry so that there are eight chiral tin atoms within the system. The structure is compared to the double ladder {[m-(R(Cl)SnCH₂CH₂)₂C₆H₄]O}₄ (11), which was prepared from the less sterically demanding ditin precursor m-(RCl₂SnCH₂CH₂)₂C₆H₄ (10). The two layers within 11 are parallel, and the molecule contains only two kinds of tin atom.

Diorganotin dications stabilized by neutral ligands in the solid state: [R2Sn(H2O)2(OPPh3)2](O3SCF3)2 (R = Me, Bu)

The synthesis of [R₂Sn(H₂O)₂(OPPh₃)₂](O₃SCF₃)₂ (R = Me (1), Bu (2)) by the consecutive reaction of R₂SnO (R = Me, Bu) with triflic acid and Ph₃PO is described. Compounds 1 and 2 feature dialkyltin(IV) dications [R₂Sn(H₂O)₂(OPPh₃)₂]^₂+ apparently stabilized by the neutral ligands in the solid state. Compounds 1 and 2 readily dehydrate upon heating at 105 and 86 °C, respectively. The preparative dehydration of 1 afforded [Me₂Sn(OPPh₃)₂(O₃SCF₃)](O₃SCF₃) (1a), which features both bidentate and non-coordinating triflate anions. In compounds 1 and 2 the ligands Ph₃PO and H₂O are kinetically labile in solution and undergo reversible ligand exchange reactions. Compounds 1, 1a and 2 were characterized by multinuclear solution and solid-state NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, conductivity measurements, thermogravimetry and X-ray crystallography.

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.

Handling of neutral information by aggregation operators

We generalize the notion of a neutral element of aggregation operators. Our construction involves tuples of values that are neutral with respect to the result of aggregation. Neutral tuples are useful to model situations in which information from different sources, or preferences of several decision makers, cancel each other. We examine many popular classes of aggregation operators in respect to their neutral sets, and also construct new aggregation operators with predefined neutral sets

Handling of neutral information by aggregation operators

We generalize the notion of a neutral element of aggregation operators. Our construction involves tuples of values that are neutral with respect to the result of aggregation. Neutral tuples are useful to model situations in which information from different sources, or preferences of several decision makers, cancel each other. We examine many popular classes of aggregation operators in respect to their neutral sets, and also construct new aggregation operators with predefined neutral sets.

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.

Handling neutral and absorbent information in aggregation processes

We generalize the concepts of neutral and absorbent elements of aggregation operators. We introduce two types of tuples of values: the neutral tuples and the absorbent tuples. the neutral tuples are useful in situations in which information from different sources, or preferences of several decision makers, cancel each other. Absorbent tuples are useful in situations in which certain decision makers may decide the outcome irrespective of the opinion of the others. We examine the most important classes of aggregation operators in respect to their neutral and absorbent tuples.

Comparison of the flexibility of eight-membered tetrasiloxane and stannasiloxane rings: a crystallographic and computational study

The syntheses and crystal structures of the eight-membered cyclo-stannasiloxanes cyclo-[t-Bu(OH)Si(OSnt-Bu₂O)₂Si(OH)t-Bu] (1) and cyclo-{t-Bu₂Si[OSn(CH₂SiMe₃)₂O]₂Sit-Bu₂} (2) as well as the synthesis of the six-membered cyclo-stannasiloxane cyclo-{t-Bu₂Si[OSn(CH₂SiMe₃)₂]₂O} (3) are reported. Compound 1 crystallizes as its trans isomer, but the cis isomer dominates in solution. In agreement with the experimentally obtained results, ab initio and DFT calculations on the model compounds cyclo-(H₂SiO)₄ (4), cyclo-[H₂Si(OSnH₂)OSiH₂] (5), cyclo-O(H₂SiOSnH₂)₂O (6), and cyclo-[H₂Si(OSiH₂)OSnH₂] (7) indicate that the energetic preference to adopt puckered structures increases and the ring flexibility decreases with an increasing number of tin atoms in the ring. The rich diversity of puckered conformations is attributed to the steric demand of the different organic substituents.

Design of linear functional observers for time-delay systems of the neutral-type

This paper presents the design of reduced-order linear functional observers for a class of linear time-delay systems of the neutral-type. The type of the observer proposed in this paper is without internal delay and its order is the same as the number of linear functions to be estimated. First, conditions for the existence of the reduced-order functional observers that are capable of asymptotically estimating any given function of the state vector are derived. Then, based on the newly derived existence conditions, a procedure is given for the determination of the observer parameters. The results derived in this paper include a range of linear systems and extend some existing results of linear functional observers to linear neutral delay systems. A numerical example is given to illustrate the design procedure.

Design of reduced-order observers for neutral time-delay systems

This paper presents a method for the design of reduced-order observers for a class of linear time-delay systems of the neutral-type. Conditions for the existence of reduced-order observers that are capable of asymptotically estimating any given function of the state vector are derived. A step-by-step design procedure is given for the determination of the observer parameters. A numerical example is given to illustrate the design procedure.

'Energetic space' : literary experience and learning

This essay is part of an interdisciplinary research project into literary aesthetics and its relationship with pedagogy. The paper brings cognitive and evolutionary scientific perspectives to bear on literary and cultural theory to address the aesthetic effect (defined as the transporting and transformative power of the literary text) and its potential personal or civic benefits. The paper offers non-transcendentalist explanations for the aesthetic experience, viewing it less as a privileged category of feeling than as an experience available to all symbolic beings. The paper also proposes an original thesis about the virtual and transformative space of reading as one that ultimately epitomises intellectual freedom. The inquiry is lent urgency by the current cultural and political climate in which not only literature but also literary studies, despite its long association with education and its prominent place in the Culture Wars, is in institutional decline.

Decoration of nitrogen vacancies by oxygen atoms in boron nitride nanotubes

Decoration of nitrogen vacancies by oxygen atoms has been studied by near-edge X-ray absorption fine structure (NEXAFS) around B K-edge in several boron nitride (BN) structures, including bamboo-like and multi-walled BN nanotubes. Breaking of B-N bonds and formation of nitrogen vacancies under low-energy ion bombardment reduces oxidation resistance of BN structures and promotes an efficient oxygen-healing mechanism, in full agreement with some recent theoretical predictions. The formation of mixed O-B-N and B-O bonds is clearly identified by well-resolved peaks in NEXAFS spectra of excited boron atoms.