Mixing and sweeping out

A weakly mixing transformationT and a sequence (d _n) are constructed such thatT is uniformly mixing on (d _n),T is uniformly sweeping out on ([αd _n]) for allα∈(0, 1), and for all rationalα∈(0, 1)T is not mixing on ([αd _n]).     

Formation, isolation and characterization of an AB-biaryl atropisomer of oritavancin

Oritavancin is a semi-synthetic glycopeptide antibiotic which is structurally related to vancomycin. When oritavancin bisphosphate is dried in vacuo with heat, a new compound forms. This new compound is stable only in the solid state and reverts to oritavancin in solution. Highly enriched samples of this compound were obtained by preparative HPLC and the structure of this compound was elucidated by using one and two-dimensional (¹H and ¹³C) NMR spectroscopy in conjunction with computer-assisted molecular modeling. It has been determined that oritavancin adopts a conformation similar to that of vancomycin in solution, while the new compound is the unnatural R-AB-biaryl atropisomer of oritavancin. This is the first observation and isolation of an AB-biaryl atropisomer in an intact member of the vancomycin family of glycopeptide antibiotics.     

Thiol–norbornene materials: Approaches to develop high Tg thiol–ene polymers

The ability to prepare high T_g low shrinkage thiol–ene materials is attractive for applications such as coatings and dental restoratives. However, thiol and nonacrylated vinyl materials typically consist of a flexible backbone, limiting the utility of these polymers. Hence, it is of importance to synthesize and investigate thiol and vinyl materials of varying backbone chemistry and stiffness. Here, we investigate the effect of backbone chemistry and functionality of norbornene resins on polymerization kinetics and glass transition temperature (T_g) for several thiol–norbornene materials. Results indicate that T_gs as high as 94 °C are achievable in thiol–norbornene resins of appropriately controlled chemistry. Furthermore, both the backbone chemistry and the norbornene moiety are important factors in the development of high T_g materials. In particular, as much as a 70 °C increase in T_g was observed in a norbornene–thiol specimen when compared with a sample prepared using allyl ether monomer of analogous backbone chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5686–5696, 2007     

Student Attitudes and Calculus Reform

This paper compares the attitudes about mathematics of students from traditionally taught calculus classes and those from a “reformed” calculus course. The paper is based on three studies, which together present a consistent picture of student attitudes about calculus reform. The reformed course appeared to violate students' deeply held beliefs about the nature of mathematics and how it should be learned. Although during their first months in the reformed course most students disliked it, their attitudes gradually changed. One and 2 years after, reform students felt significantly more than the traditionally taught students that they better understood how math was used and that they had been required to understand math rather than memorize formulas.     

Delaunay graphs are almost as good as complete graphs

LetS be any set ofN points in the plane and let DT(S) be the graph of the Delaunay triangulation ofS. For all pointsa andb ofS, letd(a, b) be the Euclidean distance froma tob and let DT(a, b) be the length of the shortest path in DT(S) froma tob. We show that there is a constantc (≤((1+√5)/2) π≈5.08) independent ofS andN such that $$\frac{{DT(a,b)}}{{d(a,b)}}< c.$$      

Anionic hyperconjugation

Although hyperconjugation involving alkyl groups to a carbocation is a well-established concept, the analogous charge delocalization generated in anions by electronegative substitution has long been a subject of controversy. We have investigated this phenomenon for the β-hydroxyethyl and β-trifluoroethyl anions using ab initio electronic structure calculations. Split valence basis sets augmented by diffuse functions were used with fully optimized geometries. Three dimensional molecular orbital plots clearly show an in-plane HOMO-LUMO mixing of a C-X σ antibonding orbital with the carbon lone pair which yields hyperconjugative π bonding in the anti conformation. Deformation density maps further demonstrate that this delocalization leads to the development of a π component as well as a previously unrecognized sigma enhancement. These results support and extend the work of Apeloig and that of Schleyer and Kos, but are in opposition to the induction hypothesis of Streitwieser and Holtz. The recent experimental determination of the acidity of (CF₃)₃CH by Tatlow $\text{et al}$ and their interpretation in terms of fluorine hyperconjugation are also in accord with this work.     

Bang-bang optimal control for the dam problem

The dam problem with general geometry is considered. Fluid is drawn from the bottomS ₁ at a ratek where 0 k N, _{S 1} k M; the objective is to minimize the total pressure of the fluid in the dam. A bang-bang principle is established for any optimal controlk ₀, that is,k ₀ = 0 on a setA andk ₀ =N on the complement setS ₁ A. In the case of a rectangular dam the structure ofA is determined and the uniqueness of the minimizerk ₀ is established.This work is partially supported by National Science Foundation Grants DMS-8501397 and DMS-8420896.     

The total synthesis of coleophomones B, C, and D

Members of the coleophomone family of natural products all possess several intriguing and challenging architectural features, as well as exhibit unusual biological activity. They, therefore, constitute attractive targets for synthesis. In this Article, we describe the total synthesis of coleophomones B (2), C (3), and D (4). The highly strained and congested 11-membered macrocycle of coleophomones B (2) and C (3) was constructed using an impressive olefin metathesis reaction. Furthermore, both of the requisite geometric isomers of the Delta(16,17) within the macrocycle could be accessed from a common precursor, facilitating a divergence that lent the coleophomone B (2)/C (3) synthesis an unusually high degree of efficiency. The synthesis of coleophomone D (4) confirmed that it exists as a dynamic mixture of isomeric forms with a different aromatic substitution pattern from the other family members.     

Simultaneous observation of coherent and incoherent resonant re-emission in the condensed phase

We report simultaneous observation of coherent resonance Raman scattering and incoherently broadened resonance fluorescence following excitation of cytochrome c in the α(0, 0) region. The influence of incoherent broadening processes on resonance Raman scattering experiments is considered.