Crystal and molecular structure of 3,5-cycloandrostan-6β-ol-17-one

The crystal and molecular structure of 3,5-cycloandrostan-6-ol-17-one has been determined by X-ray analysis,¹³C-NMR,¹H-NMR, IR and elemental analyses. The compound was obtained from dehydroepiandrosterone (DHEA) via the 3-tosyl derivative by refluxing in a butan-2-one/water mixture. The X-ray analysis shows that the planar cyclopropane ring is predominantly orientated and the formation of the C(3)-C(5) bond enables the A ring to adopt a distorted boat conformation. Spectroscopic evidence for the presence of the cyclopropane ring and the 6-hydroxy group are presented.     

Dynamic Mobility of Colloidal Particles with Thick Double Layers

The dynamic mobility spectra of several colloidal systems having a ratio of particle radius to double-layer thickness between 1 and 20 have been measured using the technique of electroacoustics. Good agreement is found between the experimental mobility spectra and the theoretical spectra generated by the computer program of Manglesdorf and White for spherical monodisperse suspensions with sizes in the neighborhood of 0.1 μm. Smaller and larger particles show some minor discrepancies which are more likely to be due to limitations of the model systems being used for the test than to any basic limitation of the theoretical analysis. Copyright 2000 Academic Press.     

Sum frequency generation at 309 nm using a violet and a near-IR DFB diode laser for detection of OH

We have used a violet diode laser at 404 nm and a distributed feedback diode laser at 1320 nm to produce 0.8 nW of radiation at 309 nm by sum frequency generation in beta-barium borate. The UV radiation was tuned mode-hop-free over 30 GHz and used to detect OH radicals produced in a microwave discharge. By chopping the UV light at 500 Hz, we observed a concentration of 2×10¹² cm^-3 with a signal to noise ratio of 30:1. Received: 16 November 2001 / Revised version: 23 January 2002 / Published online: 14 March 2002     

Gamma irradiation of electrospun poly(ε‐caprolactone) fibers affects material properties but not cell response

Fabrication of electrospun fibrous scaffolds as future medical devices is being widely researched, with particular emphasis given to their material properties and effect on cell response and differentiation. However, the vast majority of these scaffolds are sterilized via nonmedically approved methods, including submersion in ethanol and exposure to UV light. Although these techniques are adequate for laboratory‐based research, they are not sufficient for human implantation. In this case, regulatory approved, medical grade sterilization is required. In this study, we report the effects of gamma irradiation, a regulatory approved technique, on electrospun poly(ε‐caprolactone) fibers. Fabricated fibers were separately subjected to different dosages of irradiation ranging from 0 to 45 kGy and then assessed for their physicochemical properties. Gamma irradiation affected fiber properties irrespective of dosage. A dose‐dependent decrease in polymer molecular weight was observed and an increase in melting point and crystallinity reported. Similarly, irradiation had a significant effect on mechanical properties with greatest decrease in tensile strength (68%) for fibers exposed to 40 kGy. The method of sterilization had no effect on cell response. Seeded tenocytes attached to all fibers and elongated parallel to the underlying fiber direction. The results demonstrate the importance of incorporating medical grade sterilization procedures early in the research projects time line to assist translation from bench to clinic. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

The photodegradation of poly(vinyl chloride) films—IV

The concentration of residual tetrahydrofuran in cast poly(vinyl chloride) films has been varied. It is shown that the amount of tetrahydrofuran present does not affect the extent of degradation but that it does affect the relative concentration of the conjugated polyenes produced. A shift towards shorter polyenes is observed with increasing concentration of residual solvent; this effect is attributed to its ability to act as a plasticizer.     

A novel crystallization-induced diastereomeric transformation based on a reversible carbon-sulfur bond formation. Application to the synthesis of a gamma-secretase inhibitor

This paper describes a remarkably efficient process for the preparation of gamma-secretase inhibitor 1. The target is synthesized in only five steps with an overall yield of 58%. The key operation is a highly selective and practical, crystallization-driven transformation for the conversion of a mixture of tertiary benzylic alcohols into the desired sulfide diastereomer with 94:6 dr. This unprecedented process is based upon a reversible carbon-sulfur bond formation under acidic conditions.     

Photo-Fries reaction in water made selective with a capsule

The water soluble capsule formed by a deep cavity cavitand with eight carboxylic acid groups controls product distribution during photo-Fries rearrangement of naphthyl esters in water by restricting the mobility of primary singlet radical pair.     

Dynamics of a supramolecular capsule assembly with pyrene

Water-soluble octaacid cavitands (OAs) form dimeric capsules suitable for guest incorporation. Our studies reveal that the mechanism of pyrene (Py) binding involves the rapid (<1 ms) formation of the Py·OA complex followed by slower binding with the second OA. The dissociation of the capsular OA·Py·OA complex occurs with a lifetime of 2.7 s, which is 5 orders of magnitude slower than the microsecond opening/closing ("breathing") previously observed to provide access of small molecules to the encapsulated guest. These different dynamics of the capsules have a potential impact on how the chemistry of included guests could be altered.     

Exact scalar field cosmologies in a higher derivative theory

We obtain exact cosmological solutions of a higher derivative theory described by the Lagrangian L=R+2αR ² in the presence of interacting scalar field. The interacting scalar field potential required for a known evolution of the FRW universe in the framework of the theory is obtained using a technique different from the usual approach to solve the Einstein field equations. We follow here a technique to determine potential similar to that used by Ellis and Madsen in Einstein gravity. Some new and interesting potentials are noted in the presence of R ² term in the Einstein action for the known behaviours of the universe. These potentials in general do not obey the slow rollover approximation.     

Determination of the electric field gradient tensor in sodium nitroprusside using a polarized Mössbauer source

The orientation of the electric field gradient tensor at the iron nucleus in a single crystal of Na₂[Fe(CN)₅(NO)]·2H₂O has been determined using a polarized Mössbauer source of ⁵⁷Co in iron metal.