Two Efficient and Practical Syntheses of Methyl 4-Mercaptobenzoate

Two efficient syntheses of methyl 4-mercaptobenzoate are described, one utilizing the dianion of 4-bromothiophenol, the other a S_NAr reaction starting with 4-fluorobenzonitrile.     

Biochemical sensor based on a novel all-fibre cavity ring down spectroscopy technique incorporating a tilted fibre Bragg grating

A novel all-fibre cavity ring down spectroscopy technique is proposed where a tilt fibre Bragg grating (TFBG) or long-period grating (LPG) in the cavity provides sensitivity to surrounding medium. Such configuration with an LPG as the representative was theoretically analyzed. Two spectral bands were identified employable for sensing of surrounding refractive index for a weak LPG while only one band existed for a strong LPG. A TFBG, with enhanced sensitivity compared to usual LPGs, was used in a ring down cavity of 1 m constructed with 2 fibre Bragg gratings as the reflectors and the decay time changed from 220 to 450 ns when the TFBG was immersed into water from air.     

Gas-Phase Intramolecular Protein Crosslinking via Ion/Ion Reactions: Ubiquitin and a Homobifunctional sulfo-NHS Ester

Gas-phase intra-molecular crosslinking of protein ubiquitin cations has been demonstrated via ion/ion reactions with anions of a homobifunctional N-hydroxysulfosuccinimide (sulfo-NHS) ester reagent. The ion/ion reaction between multiply-protonated ubiquitin and crosslinker monoanions produces a stable, charge-reduced complex. Covalent crosslinking is indicated by the consecutive loss of 2 molecules of sulfo-NHS under ion trap collisional activation conditions. Covalent modification is verified by the presence of covalently crosslinked sequence ions produced by ion-trap collision-induced dissociation of the ion generated from the losses of sulfo-NHS. Analysis of the crosslinked sequence fragments allows for the localization of crosslinked primary amines, enabling proximity mapping of the gas-phase 3-D structures. The presence of two unprotonated reactive sites within the distance constraint of the crosslinker is required for successful crosslinking. The ability to covalently crosslink is, therefore, sensitive to protein charge state. As the charge state increases, fewer reactive sites are available and protein structure is more likely to become extended because of intramolecular electrostatic repulsion. At high charge states, the reagent shows little evidence for covalent crosslinking but does show evidence for ‘electrostatic crosslinking’ in that the binding of the sulfonate groups to the protein is sufficiently strong that backbone cleavages are favored over reagent detachment under ion trap collisional activation conditions.      

Interferometry from a scattering medium

A two-beam random interferometer is demonstrated where coupling is facilitated by a scattering medium. A modulation observed in the normalized second-order intensity frequency correlation of the transmitted light is attributed to the relative temporal delay of the two beams and is insensitive to beam alignment and spacing.     

Transition‐Metal‐Functionalized DNA Double‐Crossover Tiles: Enhanced Stability and Chirality Transfer to Metal Centers

The double crossover junction (DX) is a fundamental building block for generating complex and varied structures from DNA. However, its implementation in functional devices is limited to the inherent properties of DNA itself. Here, we developed design strategies to generate the first metal–DX DNA tiles (DX_M) by site‐specifically functionalizing the tile crossovers with tetrahedral binding pockets that coordinate Cu^I. These DX junctions bind two Cu^I ions independently at distinct sites, display greater thermal stability than native DX tiles upon metalation, and melt in a cooperative fashion. In addition, the right‐handed helical chirality of DNA is transferred to the metal centers. Our tiles display high metal ion selectivity, such that Cu^II is spontaneously reduced to Cu^I in situ. By modifying our design over three generations of tiles, we elucidated the thermodynamic and geometric requirements for the successful assembly of DX_M tiles, which have direct applicability in developing robust, stable DNA‐based materials with electroactive, photoactive, and catalytic properties.     

Detection of a systemic effect of malignancy in vivo by magnetic resonance imaging

In animals bearing tumors prolongation of spin lattice relaxation time (T1) has been detected in vitro in organs not directly affected by the malignancy. This has been termed the "Systemic Effect." In this study the possible existence of such an effect in the liver, muscle and fat of humans with lymphoma has been investigated. In vivo T1 measurements were made using a low field strength (0.08 Tesla) magnetic resonance imager. The mean liver T1 for 19 lymphoma patients with normal liver histology was 206 ms, compared with a mean of 191 ms for 61 volunteers (p less than 0.0001). Among these patients prolongation of liver T1 was related to the extent of disease elsewhere in the body. For 23 patients with Hodgkin's disease (HD) examined at the time of diagnosis, liver T1 was significantly correlated with other known markers of disease extent or activity (alkaline phosphatase level, erythrocyte sedimentation rate and the presence of systemic symptoms). No such correlations were observed among 25 patients with non-Hodgkin's lymphoma (NHL). Muscle and fat T1 was measured in 26 patients with lymphoma, 14 patients with acute leukemia and 88 volunteers. Seven of the patients with lymphoma and 2 of those with leukemia had muscle T1 values above the range observed for volunteers. Similarly, 3 patients with lymphoma and 1 with leukemia had prolonged fat T1. These findings indicate that a systemic effect of malignancy on T1 is detectable in a proportion of humans with lymphoma or leukemia.     

The nature of marbled Terra Sigillata slips: a combined μXRF and μXRD investigation

In addition to the red terra sigillata production, the largest Gallic workshop (La Graufesenque) made a special type of terra sigillata, called “marbled” by the archaeologists. Produced exclusively at this site, this pottery is characterized by a surface finish made of a mixture of yellow and red slips. Because the two slips are intimately mixed, it is difficult to obtain the precise composition of one of the two constituents without contamination from the other. In order to obtain very precise correlation at the appropriate scale between the color aspect and the elemental and mineralogical phase distributions in the slip, combined electron microprobe, X-ray micro spectroscopies and micro diffraction on cross-sectional samples were performed. The aim of this study is to discover how potters were able to produce this unique type of terra sigillata and especially this particular slip of an intense yellow color. Results show that the yellow component of marbled sigillata was made from a titanium-rich clay preparation. The color is due to the formation of a pseudobrookite (TiFe₂O₅) phase in the yellow part of the slip, the main characteristics of that structure being considered nowadays as essential for the fabrication of stable yellow ceramic pigments. Its physical properties such as high refractive indices and a melting point higher than that of most silicates widely used as ceramic colorants are indeed determinant for this kind of application. Finally, the red parts have a similar composition (elementary and mineralogical) to the one of standard red slip.