Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters

Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact.     

Lipase‐Supported Metal–Organic Framework Bioreactor Catalyzes Warfarin Synthesis

A green and sustainable strategy synthesizes clinical medicine warfarin anticoagulant by using lipase‐supported metal–organic framework (MOF) bioreactors (see scheme). These findings may be beneficial for future studies in the industrial production of chemical, pharmaceutical, and agrochemical precursors.     

Oxidative regulation of the mechanical strength of a C–S bond

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. Methods by which the intrinsic molecular strength of the constituents of a given polymeric material might be switched are therefore potentially useful both for applications in which triggered property changes are desirable, and as tests of molecular theories for bulk behaviors. Here we report that the sequential oxidation of sulfide containing polyesters (PE-S) to the corresponding sulfoxide (PE-SO) and then sulfone (PE-SO2) first weakens (sulfoxide), and then enhances (sulfone), the effective mechanical integrity of the polymer backbone; PE-S ∼ PE-SO2 > PE-SO. The relative mechanical strength as a function of oxidation state is revealed through the use of gem-dichlorocyclopropane nonscissile mechanophores as an internal standard, and the observed order agrees well with the reported bond dissociation energies of C–S bonds in each species and with the results of CoGEF modeling.

The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness.     

Operational Research and Regulation: Theory and Practice

In this Blackett Lecture, Professor Littlechild, Director General of Electricity Supply in the UK's Office of Electricity Regulation, renews acquaintance with some models he has developed over the years, introduces some models he has recently met, and discusses models that it would seem to be worthwhile developing. He concludes that for all concerned in the electricity industry, success depends on ever improving decision-making, in which OR has a vital role.     

Preparing Science Teachers in an Era of Reform: Practitioners' Perspectives of Methods Courses

With recent national calls for the reform of science education have come standards that delineate not only science content but also assessment, pedagogy, and teachers’ professional development. If teachers must teach science differently, then teacher preparation must change. This study asked 31 inservice secondary science teachers to complete a survey about topics for inclusion in a secondary science methods course. Respondents ranked a list of prespecified topics and had an opportunity to suggest other topics for inclusion in the course. Results showed that the majority of prespecified potential topics were judged important enough by these teachers to warrant inclusion in a methods course, though no individual added topic appeared on more than two surveys. Results demonstrate that these teachers believe teaching many of the traditional topics in science methods courses is still needed. In addition, they advocated the inclusion of several topics that either represent recent technological and theoretical advances, or longstanding ideas that have recently received considerable attention.     

Characterization of isolated homogeneous hypersurface singularities in ℂ4

Let V be a hypersurface with an isolated singularity at the origin in ? ⁿ⁺¹. It is a natural question to ask when V is defined by weighted homogeneous polynomial or homogeneous polynomial up to biholomorphic change of coordinates. In 1971, a beautiful theorem of Saito gives a necessary and sufficient condition for V to be defined by a weighted homogeneous polynomial. For a two-dimensional isolated hypersurface signularity V, Xu and Yau found a coordinate free characterization for V to be defined by a homogeneous polynomial. Recently Lin and Yau gave necessary and sufficient conditions for a 3-dimensional isolated hypersurface singularity with geometric genus bigger than zero to be defined by a homogeneous polynomial. The purpose of this paper is to prove that Lin-Yau’s theorem remains true for singularities with geometric genus equal to zero.     

(2 + 1) Resonance enhanced multiphoton ionization of hydrogen chloride in a pulsed supersonic jet: Vacuum wavenumbers of rotational lines with detailed band analysis for excited electronic states of HCl

A comprehensive study of the excited electronic states of HCl is reported. Using resonance enhanced multiphoton ionization ((2 + 1) REMPI) and time-of-flight mass spectrometry (TOFMS) over 120 band systems are analyzed. Supersonic jet techniques are used to prepare rotationally cold species for laser spectroscopy in the 77 000 to 96 000 cm⁻¹ region. At least 50 new electronic states are characterized as well as several features only tentatively assigned previously. A long vibrational progression consisting of 29 vibrational levels of the deeply bound V¹Σ⁺(0⁺) valence/ion-pair state is studied. We also extend the identification and analysis to high vibrational levels of low-lying Rydberg states. The assignments of [²Π_i] Rydberg state complexes are evaluated in terms of spin-orbit coupling and united-atom calculations. In several band systems, the spectra exhibit anomalous rotational line intensities and broadened linewidths which are consistent with predissociation. Multiphoton ionization with mass spectrometry permits the investigation of isotope effects as well as the appearance of fragment species associated with repulsive potential curves.