Synthesis of fused indolines by interrupted Fischer indolization in a microfluidic reactor

This study describes our development of a microfluidic reaction scheme for the synthesis of fused indoline ring systems found in several bioactive compounds. We have utilized a continuous-flow microfluidic reactor for the reaction of hydrazines with latent aldehydes through the interrupted Fischer indolization reaction to form fused indoline and azaindoline products. We have identified optimal conditions and evaluated the scope of this microfluidic reaction using various hydrazine and latent aldehyde surrogates. This green chemistry approach can be of general utility to rapidly produce indoline scaffolds and intermediates in a continuous manner.     

Spherical T-Duality

We introduce spherical T-duality, which relates pairs of the form (P, H) consisting of a principal SU(2)-bundle \({P \rightarrow M}\) and a 7-cocycle H on P. Intuitively spherical T-duality exchanges H with the second Chern class c ₂(P). Unless \({dim(M) \leq 4}\), not all pairs admit spherical T-duals and the spherical T-duals are not always unique. Nonetheless, we prove that all spherical T-dualities induce a degree-shifting isomorphism on the 7-twisted cohomologies of the bundles and, when \({dim(M) \leq 7}\), also their integral twisted cohomologies and, when \({dim(M) \leq 4}\), even their 7-twisted K-theories. While spherical T-duality does not appear to relate equivalent string theories, it does provide an identification between conserved charges in certain distinct IIB supergravity and string compactifications.     

Self‐Assembly of DNA–Oligo(p‐phenylene‐ethynylene) Hybrid Amphiphiles into Surface‐Engineered Vesicles with Enhanced Emission

Surface‐addressable nanostructures of linearly π‐conjugated molecules play a crucial role in the emerging field of nanoelectronics. Herein, by using DNA as the hydrophilic segment, we demonstrate a solid‐phase “click” chemistry approach for the synthesis of a series of DNA–chromophore hybrid amphiphiles and report their reversible self‐assembly into surface‐engineered vesicles with enhanced emission. DNA‐directed surface addressability of the vesicles was demonstrated through the integration of gold nanoparticles onto the surface of the vesicles by sequence‐specific DNA hybridization. This system could be converted to a supramolecular light‐harvesting antenna by integrating suitable FRET acceptors onto the surface of the nanostructures. The general nature of the synthesis, surface addressability, and biocompatibility of the resulting nanostructures offer great promises for nanoelectronics, energy, and biomedical applications.     

Correlation of ultrasonic scatterer size estimates for the statistical analysis and optimization of angular compounding

Ultrasonic scatterer size estimates generally have large variances due to the inherent noise of spectral estimates used to calculate size. Compounding partially correlated size estimates associated with the same tissue, but produced with data acquired from different angles of incidence, is an effective way to reduce the variance without making dramatic sacrifices in spatial resolution. This work derives theoretical approximations for the correlation between these size estimates, and the coherence between their associated spectral estimates, as functions of ultrasonic system parameters. A Gaussian spatial autocorrelation function is assumed to adequately model scatterer shape. Both approximations compare favorably with simulation results, which consider validation near the focus. Utilization of the correlation/coherence expressions for statistical analysis and optimization is discussed. Approximations, such as the invariance of phase and amplitude terms with angle, are made to obtain closed-form solutions to the derived spectral coherence near the focus and permit analytical optimization analysis. Results indicate that recommended parameter adjustments for performance improvement generally depend upon whether, for the system under consideration, the primary source of change in total coherence with rotation is phase term variation due to the change in the relative position of scattering sites, or field amplitude term variation due to beam movement.     

Statistics of ultrasonic scatterer size estimation with a reference phantom

A theoretical expression for the variance of scatterer size estimates is derived for a modified least squares size estimator used in conjunction with a reference phantom method for backscatter coefficient measurement. A Gaussian spatial autocorrelation function is assumed. Simulations and phantom experiments were performed to verify the results for backscatter and size variances. The dependence of size estimate errors upon free experimental parameters is explored. Implications of the findings for the optimization of scatterer size estimation are discussed. The utility of scatterer size parametric imaging is examined through the signal to noise ratio comparison with standard ultrasonic B-mode imaging.     

Chern Character in Twisted K-Theory: Equivariant and Holomorphic Cases

 It was argued in [25, 5] that in the presence of a nontrivial B-field, D-brane charges in type IIB string theories are classified by twisted K-theory. In [4], it was proved that twisted K-theory is canonically isomorphic to bundle gerbe K-theory, whose elements are ordinary Hilbert bundles on a principal projective unitary bundle, with an action of the bundle gerbe determined by the principal projective unitary bundle. The principal projective unitary bundle is in turn determined by the twist. This paper studies in detail the Chern-Weil representative of the Chern character of bundle gerbe K-theory that was introduced in [4], extending the construction to the equivariant and the holomorphic cases. Included is a discussion of interesting examples. Received: 10 January 2002 / Accepted: 9 December 2002 Published online: 25 February 2003 RID="⋆" ID="⋆" The authors acknowledge the support of the Australian Research Council Communicated by R.H. Dijkgraaf     

The Novikov Conjecture for Low Degree Cohomology Classes

We outline a twisted analogue of the Mishchenko–Kasparov approach to prove the Novikov conjecture on the homotopy invariance of the higher signatures. Using our approach, we give a new and simple proof of the homotopy invariance of the higher signatures associated to all cohomology classes of the classifying space that belong to the subring of the cohomology ring of the classifying space that is generated by cohomology classes of degree less than or equal to 2, a result that was first established by Connes and Gromov and Moscovici using other methods. A key new ingredient is the construction of a tautological C* _r (, )-bundle and connection, which can be used to construct a C* _r (, )-index that lies in the Grothendieck group of C* _r (, ), where is a multiplier on the discrete group corresponding to a degree 2 cohomology class. We also utilise a main result of Hilsum and Skandalis to establish our theorem.     

Quantum chemical DFT study of 4-azatricyclo [5.2.2.02,6] undecane-3,5,8-trione

Fourier-transform-Raman and infrared spectrum of 4-azatricyclo [5.2.2.0^2,6] undecane-3,5,8-trione were recorded and analyzed. The vibrational wavenumbers were examined theoretically using the Gaussian03 set of quantum chemistry codes, and the normal modes were assigned by potential energy distribution (PED) calculations. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with reported values of similar structures which makes this compound an attractive object for future studies of nonlinear optics. Optimized geometrical parameters of the compound are in agreement with similar reported structures. The red shift of the NH stretching wavenumber in the infrared spectrum from the computational wavenumber indicates the weakening of NH bond.     

The selective introduction of organometallic markers into estrogens. A-ring propargylation of β-estradiol

Introduction of the propargyl dicobalt hexacarbonyl moiety onto the estradiol A ring as a potential probe in receptor studies requires protection of the ring phenolic group, and the regio-selectivity of the attack (2- versus 4-position) depends on the bulkiness of the organometallic carbenium ion.