Heterogeneous Solution NMR Signal Amplification by Reversible Exchange

A novel variant of an iridium‐based organometallic catalyst was synthesized and used to enhance the NMR signals of pyridine in a heterogeneous phase by immobilization on polymer microbead solid supports. Upon administration of parahydrogen (pH₂) gas to a methanol mixture containing the HET‐SABRE catalyst particles and the pyridine, up to fivefold enhancements were observed in the ¹H NMR spectra after sample transfer to high field (9.4 T). Importantly, enhancements were not due to any residual catalyst molecules in solution, thus supporting the true heterogeneity of the SABRE process. Further significant improvements may be expected by systematic optimization of experimental parameters. Moreover, the heterogeneous catalyst is easy to separate and recycle, thus opening a door to future potential applications varying from spectroscopic studies of catalysis, to imaging metabolites in the body without concern of contamination from expensive and potentially toxic metal catalysts or accompanying organic molecules.     

Liquid chromatography tandem mass spectrometry determination of free and conjugated estrogens in breast cancer patients before and after exemestane treatment

We report liquid chromatographic separation with tandem mass spectrometry determination of 12 endogenous estrogens and their intact conjugates in blood and urine and its application to study effects of exemestane treatment on estrogen generation and metabolism in postmenopausal women with estrogen-dependent breast cancer. A 0.5 mL aliquot of each urine or serum sample is fractionated with solid phase extraction to a fraction of free estrogen and another fraction of their conjugates. The reversed phase LC/MS/MS determines dansylated estrogens with positive ionization and intact conjugates with negative ionization. The method provides reproducible separation and limit of detection as low as 1 pg mL⁻¹ for free estrogens and 0.03 ng mg⁻¹ creatinine for the conjugates in serum and urine samples. The method enabled us to acquire unique concentration profiles of 12 endogenous estrogens and their intact conjugates in 30 breast cancer patients before and after one month of exemestane treatment. Exemestane suppressed total serum and urinary estrogens by 11–97% (P < 0.0001) and 8.7–91% (P < 0.0001), respectively. Specifically, these data show that exemestane preferentially suppressed E1, E1-3S, E1-3G, and E2-17G more than other estrogens. Linear regression analysis of estrogen concentrations before and after treatment showed correlation coefficients of 0.8385 (n = 289, P < 0.0001) and 0.8863 (n = 360, P < 0.0001). This study provides urinary and blood estrogen concentration profiles in breast cancer patients to demonstrate the effect of exemestane on estrogen generation, supporting inhibition of aromatase activity.     

The morphology of tin cluster assembled films and the effect of nitrogen

Thin films produced by depositing tin clusters with sizes between 5 and 10 nm onto silicon nitride substrates were found to be highly coalesced resulting in grains with sizes ~30 nm. Exposing the clusters to nitrogen before they were deposited significantly reduced the coalescence between them and resulted in granular films where the clusters mostly retained their shape. This is due to a small amount of tin nitride forming in the clusters. The coalesced and granular films were used to fabricate tin oxide gas sensors. This was done by depositing the two types of films onto silicon nitride chips and then oxidising them by baking at 250 °C for 24 h. It was found that the sensors composed of uncoalesced clusters were much more sensitive to hydrogen. This was attributed to the smaller grain size and the larger surface area of the granular films.     

Locally Asplund Preduals of Spaces of Holomorphic Functions

Defant [5] introduced the local Radon–Nikodym property for duals of locally convex spaces. This is a generalization of Asplund spaces as defined in Banach space theory. In this paper we generalise Dunford"s Theorem [7] to Banach spaces with Schauder decompositions and apply this result to spaces of holomorphic functions on balanced domains in a Banach space. This revised version was published online in June 2006 with corrections to the Cover Date.     

On a problem of Byrnes concerning polynomials with restricted coefficients, II

As in the earlier paper with this title, we consider a question of Byrnes concerning the minimal length of a polynomial with all coefficients in which has a zero of a given order at . In that paper we showed that for all and showed that the extremal polynomials for were those conjectured by Byrnes, but for that rather than . A polynomial with was exhibited for , but it was not shown there that this extremal was unique. Here we show that the extremal is unique. In the previous paper, we showed that is one of the 7 values or . Here we prove that without determining all extremal polynomials. We also make some progress toward determining . As in the previous paper, we use a combination of number theoretic ideas and combinatorial computation. The main point is that if is a primitive th root of unity where is a prime, then the condition that all coefficients of be in , together with the requirement that be divisible by puts severe restrictions on the possible values for the cyclotomic integer .

     

S-pixyl analogues as photocleavable protecting groups for nucleosides

Several analogues of the 9-phenylthioxanthyl (S-pixyl) photocleavable protecting group have been synthesized, containing substituents on the 9-aryl ring and on the thioxanthyl backbone. Each analogue protected the 5'-hydroxy moiety of thymidine in good to excellent yield. The protected substrates were deprotected in 1:1 water:acetonitrile with irradiation at 300 nm, resulting in recovered thymidine in excellent yield, except for the nitro-substituted analogues which gave substantially lower yields. Substrates with 2,7-dibromo or 3-methoxy substitution on the thioxanthyl backbone were also deprotected efficiently with irradiation at 350 nm. Shorter irradiation times were observed in the less nucleophilic solvent mixture of 1:9 trifluoroethanol:acetonitrile, with no formation of secondary photooxidation products. Photodeprotection with high yields was also achieved in the absence of solvent, with no secondary photoproducts.     

Conical harmonic generation in isotropic materials

A novel class of nonlinear optical processes is described in which radiation at the nth harmonic is generated through the use of a (2n+1)-order nonlinearity. Utilizing an odd-order nonlinearity, this process allows for the generation and amplification of both odd- and even-order harmonics in isotropic materials. Additionally, this process can always be phase matched in normal-dispersion materials without the use of birefringence. Experimental results are presented in which conical third-harmonic emission is generated from a sapphire sample.     

Honeycomb pattern formation by laser-beam filamentation in atomic sodium vapor

We have observed transverse pattern formation leading to highly regular structures in both the near and far fields when a near-resonant laser beam propagates without feedback through an atomic sodium vapor. One example is a regular far-field honeycomb pattern, which results from the transformation of the laser beam within the vapor into a stable three-lobed structure with a uniform phase distribution and highly correlated power fluctuations. The predictions of a theoretical model of the filamentation process are in good agreement with these observations.     

Beyond the absorption-limited nonlinear phase shift with microring resonators

We show that the nonlinear phase shift produced by a ring resonator constructed from a given nonlinear optical material can be greater than the phase shift produced by a single pass through an infinite length of the same material when linear and nonlinear absorption are taken into consideration. The figure of merit (defined by the phase shift times the throughput) also improves for the ring resonator over that of the native nonlinear absorbing material. We finally show that these benefits of using the ring resonator as a nonlinear phase-shifting element can enhance the switching characteristics of a Mach-Zehnder interferometer.