Ti-based subunit couplings: a concise,modular synthesis of routiennocin methyl ester

A short total synthesis of routiennocin methyl ester is reported. The key reaction is the direct acylation of a titanacyclopropane with valerolactone to give a ketone.     

Luminescence studies of polymer matrices. III. Characterization and evaluation of acrylic acid‐based polymers as hosts for a phosphorescent coding system

The phosphorescence characteristics of naphthyl labelled poly(acrylic acid) film samples have been studied as a function of temperature, with a view to investigating the effect of matrix control on the level of triplet emission observed. Two relaxations, which serve to deactivate the excited triplet states have been detected from phosphorescence lifetime measurements: the α (or glass) and the βtransition (which can be associated with the onset of rotation of the carboxylic acid group). Investigation of the emission from 2‐benzoyl naphthalene dispersed within both an acrylic acid‐methyl methacrylate copolymer and a PAA film, respectively, has revealed that the more intense, longer‐lived phosphorescence results from the modified polymer. This is considered to reflect the existence of (i) hydrogen‐bonding interactions induced by the presence of carboxylic acid groups which serve to form a rigid matrix and (ii) intramolecular aggregates of methyl methacrylate units which create hydrophobic‐rich pockets, capable of sustaining intense phosphorescence at room temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2127–2136, 1999     

Nuclear orbiting and anomalies in nuclear reactions

In this paper, we report our measurements of back-angle oxygen and carbon particle yields from ¹⁶O+⁸⁹Y, ¹²C+⁹³Nb reactions forming the same compound nucleus ¹⁰⁵Ag at the same excitation energy and spin distribution. We find anomalously large oxygen yield and entrance channel dependence at high excitation energies from ¹⁶O+⁸⁹Y reaction implying formation of a dinuclear orbiting complex. Possible connection between nuclear orbiting and fast fission is also discussed.     

Activated T cells regulate bone loss and joint destruction in adjuvant arthritis through osteoprotegerin ligand

Bone remodelling and bone loss are controlled by a balance between the tumour necrosis factor family molecule osteoprotegerin ligand (OPGL) and its decoy receptor osteoprotegerin (OPG). In addition, OPGL regulates lymph node organogenesis, lymphocyte development and interactions between T cells and dendritic cells in the immune system. The OPGL receptor, RANK, is expressed on chondrocytes, osteoclast precursors and mature osteoclasts. OPGL expression in T cells is induced by antigen receptor engagement, which suggests that activated T cells may influence bone metabolism through OPGL and RANK. Here we report that activated T cells can directly trigger osteoclastogenesis through OPGL. Systemic activation of T cells in vivo leads to an OPGL-mediated increase in osteoclastogenesis and bone loss. In a T-cell-dependent model of rat adjuvant arthritis characterized by severe joint inflammation, bone and cartilage destruction and crippling, blocking of OPGL through osteoprotegerin treatment at the onset of disease prevents bone and cartilage destruction but not inflammation. These results show that both systemic and local T-cell activation can lead to OPGL production and subsequent bone loss, and they provide a novel paradigm for T cells as regulators of bone physiology.     

Determination of (210)Pb, (210)Bi and (210)Po in natural waters and other materials by electrochemical separation

An improved method for determination of (210)Pb, (210)Bi and (210)Po in both natural waters and solid materials has been developed. Polonium-210 is spontaneously plated onto a silver disc from dilute hydrochloric acid medium. Bismuth-210 is then electro-deposited onto a platinum gauze cathode directly from the same solution, with a graphite rod as anode. Finally, (210)Pb is electro-deposited from a fluoroborate medium onto the same platinum gauze, used as the anode. All three nuclides are subsequently measured by standard low-level alpha and beta counting techniques. The speed of this method (approximately 6 hr per sample after pretreatment) is a distinct advantage over existing techniques, as (210)Bi must be quickly separated from (210)Pb because of its 5.02-day half-life. Another advantage of this method is that the chemical form of the sample solution is suitable for use of established separation schemes for determining other decay-series isotopes (U, Th, Pa, etc.) after the three short-lived nuclides have been processed.     

Ion exchange removal of cesium from Hanford tank waste supernates with SuperLig® 644 resin

SuperLig^Ò 644 ion exchange resin is currently being evaluated for cesium (¹³⁷Cs) removal from radioactive Hanford tank waste supernates as part of the River Protection Project. Testing was performed with actual Hanford tank wastes of widely different compositions using two identical ion exchange columns connected in series each containing approximately 5.5-6.5 ml of SuperLig 644 resin. The ion exchange columns utilized the same resin material that was eluted between the column tests. This was done to demonstrate the performance of the SuperLig 644 resin for cesium removal from waste samples of different compositions, determine the loading and elution profiles, and to validate design assumptions for full-scale column performances. Decontaminated product solutions generated at the same operating temperature and constant residence times (bed volumes per hour) exhibited the same chemical compositions as their feed samples. The compositions of eluate solutions were generally as expected with the exception of uranium and total organic carbon, which where concentrated by the resin. Development of a pretreatment method for the SuperLig 644 resin has been critical to successful column operation with different waste solutions.     

Modulation techniques and applications in comprehensive two-dimensional gas chromatography (GC x GC)

More than a decade after Phillips' first published work this article reviews recent developments in comprehensive two-dimensional gas chromatography (GC x GC). Special attention is devoted to the further development and diversity of modulation devices. These include heated sweepers, cryofocused modulators, and a variety of diaphragm valve-switching strategies. It is demonstrated that all modulation approaches can be very well suited to GC x GC, depending on the particular application. Diaphragm-valve modulation is very powerful for volatile organic compounds. Slotted heater and cryofocused modulation are preferred for samples that contain non-volatile components. Applications ranging from petroleum to environmental and biological samples are illustrated. Extension of the technique to GC x GC-mass spectrometry (MS) is also discussed and trends for future research activity are pointed out.     

Fluorine insertion reactions into pre-formed metal oxides

Fluorine insertion reactions have been shown to be capable of modifying the physical properties of metal oxide materials, as a result of the structural and electronic consequences of fluorine insertion. This has been applied to copper oxide systems and has led to an enhanced understanding of the requirements for superconductivity, and more recently to other magnetic metal oxide systems where it has been shown to tune the magnetic properties of these materials. This review focuses on some important aspects of research on low temperature fluorine insertion reactions into pre-formed metal oxides, since 1998, and reports some new results.     

Optimization and application of the large volume on-column introduction (LOCI) technique for capillary GC with preliminary on-line capillary solvent distillation/concentration

This report describes an on-line capillary GC injection system which enables on-column injection of a hundred or more microliters, and yields separations comparable with those obtained from on-column injection of 1–2 microliters of solutions a hundred times more concentrated. Precision, carry-over, linearity, and discrimination are comparable with those of classical sample-introduction techniques. A selection of polar and high boiling compounds has been examined, and excellent peak shapes obtained for hundreds of injections. Initial results indicate that maintenance and long-term reproducibility will also be comparable with those of classical techniques. The instrument utilizes a version of the large volume on-column injector with solvent diversion described in an earlier communication, with the addition of a method for independent heating of the retention gap. This modification reduces the effects of activity in the retention gap and improves the capability of the technology to handle complex mixtures. It also increases reliability and system lifetime, fits readily into most GC ovens, is easily automated, and should be compatible with all capillary GC detectors.