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New limit on CPT violation

A search for antiproton decay has been made at the Fermilab Antiproton Accumulator. Limits are placed on fifteen antiproton decay modes. The results are used to place limits on the characteristic mass scale m(X) that could be associated with CPT violation accompanied by baryon number violation.

Journal Article↗

Redetermination of the trigonal prismatic complex tris(cis-1,2-diphenylethylene-1,2-dithiolato)rhenium.

The first trigonal prismatic molecular compound characterized by single-crystal X-ray diffraction, [Re(C14H10S2)3], has been redetermined using modern laboratory equipment. The new experiment reaffirms the results of the original. Since then, numerous tris-dithiolene complexes have been structurally characterized, having geometries ranging from trigonal prismatic to nearly octahedral. An examination of the coordination geometries of these structures is included.

Journal Article↗

Ultrasound assessment of the suspected scaphoid fracture.

A prospective study of 111 patients thought to have sustained a recent scaphoid fracture on clinical grounds but who were radiologically negative was undertaken over a period of 7 months. All such patients were subjected to ultrasound scanning within a week of their injury under double blind conditions. All patients were re-X-rayed 2-3 weeks after their injury. The authors' results suggest that ultrasonic diagnosis of the possibly fractured scaphoid is unreliable.

Adolescent↗

Prevention of bony fluorosis in aluminum smelter workers. A 15-year retrospective study of fluoride excretion and bony radiopacity among aluminum smelter workers -- Pt. 4.

1. Fifty six aluminum smelter workers with 10 to 43 years' occupational exposure, and who had been previously studied medically, were re-x-rayed. Average urinary fluoride concentrations since 1960 were estimated to range from 2.78 mg/liter preshift and 7.71 mg/liter postshift. 2. Roentgenographic studies in 1960-66 and 1974 failed to reveal any evidence of fluoride associated bony change. 3. Although these workers represent a self-selected group, their magnitude and duration of exposure far outweighs any other group working at present or in the past at this plant. The implication that they have uniformly self-selected as fluoride resistant individuals is improbable. 4. These data indicate that group post-shift ur a long period is not associated with enhanced risk of bony fluorosis. If preshift urinary fluoride concentrations are less than 4 mg/l, the same results appears to apply.

Adult↗

Complexes having the fac-[M(CO)3]+ core (M=Tc, Re) useful in radiopharmaceuticals: X-ray and NMR structural characterization and density functional calculations of species containing two sp3 N donors and one sp3 O donor.

Radiopharmaceuticals containing the "fac-[M(CO)3]+ " core (M=99mTc, 186Re, or 188Re) have potential as diagnostic or therapeutic agents. Complexes with this core with sp3 amine donors have received little attention. We have studied adducts formed by ENDACH2 (HO2CCH2NHCH2CH2NHCH2CO2H) and ENACH (NH2CH2CH2NHCH2CO2H). Re(CO)3(ENDACH)-A (1A) and Re(CO)3(ENDACH)-B (1B) isomers were obtained by the reaction of ENDACH2 with Re(CO)5Cl. Re(CO)3(ENAC) (2) was obtained by the reaction of ENACH with aqueous [Re(CO)3(H2O)3]+. From single-crystal X-ray data, the three new neutral complexes, 1A, 1B, and 2, have a six-coordinate, pseudo-octahedral Re center with facially coordinated carbonyl ligands. ENDACH- and ENAC- bind facially to Re through both amine nitrogens and one carboxyl oxygen, forming two five-membered chelate rings. The Re(CO)3(ENDACH) isomers have an uncoordinated, dangling -CH2CO2H group, which is an ideal coupling site for attachment to biomolecules. The isomers differ by the configuration of the NH center bearing this dangling group. The H atom of the amine (N2) is endo (near the carbonyl ligands in the basal plane) in 1A and exo (away from carbonyl ligands) in isomer 1B. Isomers reach equilibrium (1A:1B, 70:30) after 3 days at high pH. Density functional structure optimizations were performed for isolated molecules of the type Tc(I)/Re(I)(CO)3(N2O): [Re(CO)3(NH3)2(H2O)]+, [Tc(CO)3(NH3)2(H2O)]+, [Re(CO)3(EN)(H2O)]+ (EN, ethylenediamine), [Tc(CO)3(EN)(H2O)]+, and various models for 1A, 1B, and 2. The computed structures are in good agreement with the X-ray structures. The theoretical and experimental Re-N bond distances usually agree within 0.045 A. The total electronic energy values for the computed 1A and 1B models differ by 0.815 kcal mol(-1), giving an isomer ratio of 80:20, in good agreement with the 1A/1B ratio (70:30) found.

Crystallography, X-Ray↗

Electroswitchable photoluminescence activity: synthesis, spectroscopy, electrochemistry, photophysics, and X-ray crystal and electronic structures of [Re(bpy)(CO)3(C[triple bond]C[bond]C6H4[bond]C[triple bond]C)Fe(C5Me5)(dppe)][PF6](n) (n = 0, 1).

A novel heterobimetallic alkynyl-bridged complex, [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C)Fe(C(5)Me(5))(dppe)], 1, and its oxidized species, [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C)Fe(C(5)Me(5))(dppe)][PF(6)], 2, have been synthesized and their X-ray crystal structures determined. A related vinylidene complex, [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond](H)C[double bond]C)Fe(C(5)Me(5))(dppe)][PF(6)], 3, has also been synthesized and characterized. The cyclic voltammogram of 1 shows a quasireversible reduction couple at -1.49 V (vs SCE), a fully reversible oxidation at -0.19 V, and a quasireversible oxidation at +0.88 V. In accord with the electrochemical results, density-functional theory calculations on the hydrogen-substituted model complex Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C)Fe(C(5)H(5))(dHpe) (Cp = C(5)H(5), dHpe = H(2)P[bond](CH(2))(2)[bond]PH(2)) (1-H) show that the LUMO is mainly bipyridine ligand pi* in character while the HOMO is largely iron(II) d orbital in character. The electronic absorption spectrum of 1 shows low-energy absorption at 390 nm with a 420 nm shoulder in CH(2)Cl(2), while that of 2 exhibits less intense low-energy bands at 432 and 474 nm and additional low-energy bands in the NIR at ca. 830, 1389, and 1773 nm. Unlike the related luminescent rhenium(I)-alkynyl complex [Re(bpy)(CO)(3)(C[triple bond]C[bond]C(6)H(4)[bond]C[triple bond]C[bond]H)], 4, complex 1 is found to be nonemissive, and such a phenomenon is attributed to an intramolecular quenching of the emissive d pi(Re) --> pi*(bpy) (3)MLCT state by the low-lying MLCT and LF excited states of the iron moiety. Interestingly, switching on of the luminescence property derived from the d pi(Re) --> pi*(bpy) (3)MLCT state can be demonstrated in the oxidized species 2 and the related vinylidene analogue 3 due to the absence of the quenching pathway.

Journal Article↗

Re-refinement of the X-ray crystal structure of bovine lens leucine aminopeptidase complexed with bestatin.

Bestatin, (2S,3R)-3-amino-2-hydroxy-4-phenylbutanoyl-L-leucine, has been incorrectly modelled in the previously reported structure of the complex between bovine lens leucine aminopeptidase (blLAP) and bestatin. In the previously reported structure, the C2 of bestatin was modelled and refined in the R configuration instead of the correct S configuration. The structure of the blLAP-bestatin complex has been re-refined after remodelling bestatin in its correct stereochemistry.

Animals↗

High chromosomal sensitivity of Chinese hamster xrs 5 cells to restriction endonuclease induced DNA double-strand breaks.

The cytogenetic effects of restriction endonucleases (RE) and X-rays were examined in the radiosensitive mutant Chinese hamster cell line xrs 5 and its normal parental line CHO K1. Cells were permeabilized with Sendai virus and exposed to Pvu II and Eco RV which induce blunt-ended double-strand breaks (dsb) in the DNA of cells, or Bam H1 and Eco R1 which induce cohesive-ended dsb with a four-base overlap. Treated cells were then assayed for the presence of metaphase chromosomal aberrations by sampling at multiple fixation times and in experiments where cells were exposed to graded series of RE concentrations. Exposure to X-rays or RE causing blunt-ended dsb was found to be between two and three times more effective in xrs 5 than in CHO K1 cells. We interpret this higher chromosomal sensitivity of xrs 5 cells as reflecting the reported defect in dsb repair in xrs 5. Both xrs 5 and CHO K1 cells yielded less aberrations after exposure to Bam H1 or Eco R1 than after exposure to Pvu II or Eco RV, confirming our previous results and demonstrating that cohesive-ended dsb are less damaging than blunt-ended dsb. Multiple fixation time experiments showed that the higher sensitivity of xrs 5 was evident at several different sampling times after treatment. Similarly the low yield of aberrations after exposure of cells to Bam H1 was evident at all sampling times. Overdispersion of chromosomal aberrations was observed in samples exposed to RE. This is thought to be due to a non-uniform permeabilization of the cell population to RE. Our results indicate that RE-induced dsb are handled by cells in a similar way to those arising during X-ray exposure.

Animals↗

Re-irradiation tolerance of rat spinal cord to fractionated X-ray doses.

Experiments were performed to assess the re-irradiation fractionation sensitivity in the rat cervical spinal cord. Animals were given initially three daily fractions of 9 Gy representing 75% of tolerance at the ED50 level. After an interval of 20 weeks, they were re-irradiated with graded doses of X-ray in single, 2, 5, 10 and 20 daily fractions, or a single retreatment top-up dose of 12.8 Gy (equivalent to 80% of retreatment tolerance) followed by doses in 1, 2, 4, 10 and 20 daily fractions. The end-point was paralysis of the forelimbs secondary to white matter necrosis. Latent periods to paralysis ranged from 188 to 245 days from initial irradiation, or from 48 to 105 days from re-irradiation. For a given fractionated retreatment schedule, shorter latent times were observed in animals re-irradiated to higher total doses. The re-irradiation ED50 values for single, 2, 5, 10 and 20 fractions were 14.0 (95% CI 13.3, 14.2), 20.5 (19.9, 21.2), 29.1 (28.0, 30.1), 36.3 (35.1, 37.4) and 47.8 Gy (46.2, 48.3), respectively. For re-irradiations with a 12.8 Gy top-up dose followed by doses in single, 2, 4 and 20 fractions, the retreatment ED50 values excluding the 12.8 Gy top-up dose were 4.5 (95% CI 3.0, 5.4), 6.5 (5.6, 7.3), 7.0 (5.0, 8.1) and 10.9 Gy (8.9, 12.5), respectively.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗

Enhancements of energetic particles near the heliospheric termination shock.

The spacecraft Voyager 1 is at a distance greater than 85 au from the Sun, in the vicinity of the termination shock that marks the abrupt slowing of the supersonic solar wind and the beginning of the extended and unexplored distant heliosphere. This shock is expected to accelerate 'anomalous cosmic rays', as well as to re-accelerate Galactic cosmic rays and low-energy particles from the inner Solar System. Here we report a significant increase in the numbers of energetic ions and electrons that persisted for seven months beginning in mid-2002. This increase differs from any previously observed in that there was a simultaneous increase in Galactic cosmic ray ions and electrons, anomalous cosmic rays and low-energy ions. The low-intensity level and spectral energy distribution of the anomalous cosmic rays, however, indicates that Voyager 1 still has not reached the termination shock. Rather, the observed increase is an expected precursor event. We argue that the radial anisotropy of the cosmic rays is expected to be small in the foreshock region, as is observed.

Journal Article↗