Improving Physical Properties via C?H Oxidation: Chemical and Enzymatic Approaches

Physicochemical properties constitute a key factor for the success of a drug candidate. Whereas many strategies to improve the physicochemical properties of small heterocycle‐type leads exist, complex hydrocarbon skeletons are more challenging to derivatize because of the absence of functional groups. A variety of C H oxidation methods have been explored on the betulin skeleton to improve the solubility of this very bioactive, yet poorly water‐soluble, natural product. Capitalizing on the innate reactivity of the molecule, as well as the few molecular handles present on the core, allowed oxidations at different positions across the pentacyclic structure. Enzymatic oxidations afforded several orthogonal oxidations to chemical methods. Solubility measurements showed an enhancement for many of the synthesized compounds.     

PEGylated Luminescent Gold Nanoclusters: Synthesis,Characterization, Bioconjugation,and Application to One‐ and Two‐Photon Cellular Imaging

Biocompatible, near‐infrared luminescent gold nanoclusters (AuNCs) are synthesized directly in water using poly(ethylene glycol)‐dithiolane ligands terminating in either a carboxyl, amine, azide, or methoxy group. The ≈1.5 nm diameter AuNCs fluoresce at ≈820 nm with quantum yields that range from 4–8%, depending on the terminal functional group present, and display average luminescence lifetimes approaching 1.5 μs. The two‐photon absorption (TPA) cross‐section and two‐photon excited fluorescence (TPEF) properties are also measured. Long‐term testing shows the poly(ethylene glycol) stabilized AuNCs maintain colloidal stability in a variety of media ranging from saline to tissue culture growth medium along with tolerating storage of up to 2 years. DNA and dye‐conjugation reactions confirm that the carboxyl, amine, and azide groups can be utilized on the AuNCs for carbodiimide, succinimidyl ester, and Cu^I‐assisted cycloaddition chemistry, respectively. High signal‐to‐noise one‐ and two‐photon cellular imaging is demonstrated. The AuNCs exhibit outstanding photophysical stability during continuous‐extended imaging. Concomitant cellular viability testing shows that the AuNCs also elicit minimal cytotoxicity. Further biological applications for these luminescent nanoclustered materials are discussed.     

Structure property correlations in alcohols through two-photon absorption cross-section measurements

Two-photon absorption (TPA) cross-sections of neat alcohols are shown to be a femtosecond laser measurable property with useful structure property correlations that are directly correlated to the self-phase modulation of the alcohol in question. The amount of self-phase modulation is shown to be a molecular structure dependent property. The real and the imaginary components of the second-order hyperpolarizability are thus shown to be interrelated. Such TPA measurements prove that it is not possible to predict two-photon absorption properties by simple doubling the wavelengths of one-photon absorption spectra.     

Motion of test particles around domain walls

We present a detailed analysis of the motion of test particles around domain walls. The study of the trajectories of the test particles has been done using the Hamilton-Jacobi formalism. In most of the cases we show that the particles can not be trapped by the walls.     

Multiphoton coherent control in complex systems

Control of multiphoton transitions is demonstrated for a multilevel system by generalizing the instantaneous phase of any chirped pulse as individual terms of a Taylor series expansion. In the case of a simple two-level system, all odd terms in the series lead to population inversion while the even terms lead to self-induced transparency. The results hold for multiphoton transitions that do not have any lower-order photon resonance or any intermediate virtual state dynamics within the laser pulse width.     

A convenient palladium catalyzed synthesis of symmetric biaryls, biheterocycles and biaryl chiral diamides

A series of symmetrical diamido biaryls has been synthesized in good yield by direct homocoupling of iodoarylbenzamides by palladium-catalysis. No cross product has been isolated from the reaction mixture of two different iodoarylbenzamides under similar conditions. However, only in the case of 2-iodo-N-phenylbenzamide, the intramolecularly coupled product phenanthridone has been isolated as a minor product along with the major intermolecularly coupled product. Biphenyl chiral diamides have been synthesized by this coupling method. This coupling reaction also works well with the reductive dimerization of functionalized heterocyclic compounds. Thus 6,6′-dipivaloylamino-3,3′-bipyridine and 6,6′-dimethyl-2,2′-bipyridine have been efficiently synthesized. In two cases, the X-ray crystal structures have been solved to establish the structures of symmetrical and chiral diamido biaryls and their supramolecular networks.     

Band structures of121,123I

The band structures of^{121, 123}I nuclei have been studied using a version of the particle-rotor-model in which the experimental excitation energies of the neighbouring (A-1) cores can be fed directly as input parameters. The calculations have been carried out with axially symmetric Nilsson potential with both prolate and oblate deformations. The parameters of the model have been chosen from earlier theoretical work and experimental odd-even mass differences. Only the Coriolis attenuation factor has been treated as adjustable parameter. The theoretical band structures are in very good agreement with the available experimental data.     

On the hexadecapole collective motion in spherical nuclei

The hexadecapole-collective motion in spherical nuclei is discussed. Numerical calculations are presented and compared with available experimental data.     

Anomaly in electron channeling due to imperfections produced thermally in a potassium chloride crystal

Lattice imperfections were produced in KCl crystals by a thermal process. The heat treated specimen was irradiated with 50 KeV electrons and the corresponding range of electrons in the crystal has been estimated. It was found that the electron range in the crystal depends upon the temperature of heat treatment, being a decreasing function of this temperature up to about 625 K, above which it becomes an increasing function. This anomaly has been explained in terms of dissolution of vacancies through dislocation loops.     

A study of the vestigial records of cosmic rays in lunar rocks using a thick section technique

An experimental technique has been developed for systematic measurements of fossil tracks along selected planes cut from grains and rocks. With controlled etching, the technique allows successive revelation of tracks in different minerals in the same section, a typical sequence being olivine, anorthite, clinopyroxene. It thus becomes possible to study precisely the cosmic ray track density variations over dimensions much greater than those of individual crystals. The technique also provides accurate information on the relative recording characteristics of different minerals present in a rock and cosmic ray tracks can be studied with a minimum interference of tracks due to spontaneous fission of uranium and transuranic elements. Continuous chains of sections, each section measuring approximately 1 cm., have been cut along several different planes in fifteen rocks from Mare Tranquillitatis, Oceanus Procellarum and Fra Mauro region. The cosmic ray track measurements from these sections have provided dramatic evidence for a number of processes affecting lunar rocks. The statistical, and non-uniform nature of erosion by micrometeorite bombardment can be seen in sections intersecting exposed surface which show regions of very steep track density gradients interspersed with eroded regions having lower track densities. The thick section technique permits determination of the energy spectrum of VH nuclei from track density gradients that extend over distances limited only by the dimensions of the rock, and, more important, in samples of identical orientation. The latter is particularly important in higher energy regions (deeper within the rock) where variations in crystal orientation cause track density differences of the same order as real changes in the gradient. Also in the near surface regions of rocks where low energy particles produce steep track density gradient, the thick section method has proved indispensable since it permits accurate depth determinations not possible in the spot sampling procedure. In this paper the technique of studying track profiles in thick sections is described. Although developed primarily for studying lunar samples, the thick section technique is also useful for similar studies in meteorites, particularly for gas-rich meteorites containing irradiated grains. In contrast to single grain studies, thick sections preserve the grain boundaries and permit accurate depth—density measurements. In addition thick section studies have revealed occasional large uniformly irradiated lithic fragments which would not have been possible to discover by spot sampling methods.