Chemical reactivity and surface-enhanced raman scattering

A mechanism is proposed for surface-enhanced Raman scattering for pyridine which explains the enhancement, the anodizalion “activation”, the significance of silver, the photographitization of coordinated pyridine and formate, the participation of surface roughness, and the irreversibly held yet liquid-like nature of surface pyridine.     

Spectroscopic research on ultrahigh pressure (UHP) macrodiamond at Copeton and Bingara NSW, Eastern Australia

Millions of macrodiamonds were mined from Cenozoic placers across Eastern Australia, 98% from within the Copeton and Bingara area (85 km across) in the Phanerozoic New England region of New South Wales (NSW). Raman spectroscopy of inclusions in uncut diamond, from the Copeton and Bingara parcels, identifies them as ultrahigh pressure (UHP) macrodiamond formed during termination of subduction by continental collision. Infrared spectral properties of the two parcels are critically similar in terms of nitrogen abundance (low in zoned diamond, high in unzoned diamond), requiring a pair of different growth mechanisms/protoliths. Within each parcel, the degrees of nitrogen aggregation are relatively strong and coherent, but they are so different from each other (moderate aggregation for Bingara, strong for Copeton) that the two parcels require separate primary and local sources. The local sources are post-tectonic alkali basaltic intrusions which captured UHP minerals (garnet, pyroxene, diamond) from eclogite-dominated UHP terranes (density stranded at depth-mantle, lower crust). X-ray diffraction studies on Copeton diamond indicate a normal density, despite previous reports of anomalously high density. For non-fluorescent diamond, a 2nd order Raman peak, which is prominent in theoretical perfect diamond and in African cratonic diamond, is suppressed in Copeton and Bingara UHP macrodiamond. Pervasive deformation during macrodiamond growth probably causes this suppression, the strong nitrogen aggregation, and the exceptional durability documented through industrial use.     

A Raman microprobe study of melt inclusions in kimberlites from Siberia, Canada, SW Greenland and South Africa

The geometries, energies and vibrational frequencies of various polyborates in both gaseous and aqueous phase were calculated at the B3LYP/aug-cc-pVDZ level. The calculated total symmetrical stretching Raman shifts of B(OH)(3), B(OH)(4)(-), B(2)O(OH)(4), B(2)O(OH)(5)(-), B(2)O(OH)(6)(2-), B(3)O(3)(OH)(3), B(3)O(3)(OH)(4)(-), B(3)O(3)(OH)(5)(2-), B(3)O(3)(OH)(6)(3-), B(4)O(5)(OH)(4)(2-) and B(5)O(6)(OH)(4)(-) were assigned to 877.40, 735.33, 785.22, 792.90, 696.79, 587.72, 599.06, 740.16, 705.01, 551.67 and 521.04cm(-1), respectively. The results can be used as the characteristic frequency for polyborates in aqueous phase at room temperature. At least six types of polyborates B(OH)(3), B(OH)(4)(-), B(3)O(3)(OH)(4)(-), B(3)O(3)(OH)(5)(2-), B(4)O(5)(OH)(4)(2-) and B(5)O(6)(OH)(4)(-), occur in aqueous solutions at ambient temperature. The chemical species distribution and the relevant interaction mechanisms among polyborates in the solutions were also suggested.     

Raman spectra of forsterite and fayalite at high pressures and room temperature

Abstract

Raman spectra of the two pure end-members of olivine (forsterite and fayalite) were studied at high pressures and room temperature in a diamond-anvil cell using both single-crystals and polycrystalline samples in pressure mediums of either an ethanol-methanol mixture or H₂O. Variations with pressure were studied up to 170kbar for fayalite and to 300kbar for forsterite. Two intensive Raman bands of fayalite were definitely observable at high pressures, but only one of them can be reliably determined. Both have a linear variation within experimental uncertainty. Because of interference from the high spectral background, we found that nearly all the weak bands of forsterite could not be reliably determined at high pressures. However, the pressure variations of all bands of forsterite which can be reliably determined are non-linear. The rates of frequency change for the intense bands of forsterite determined in the present experiment are consistent with those of natural forsterites determined by Besson et al. ¹ and Gillet et al. ², but are in a slight discordance with those reported by Chopelas³. Furthermore, there is no evidence for the olivine ? spinel phase transition occurring at room temperature.     

Measurements of fluoride in bone biopsies by neutron activation analysis for the clinical study of osteoporosis

A procedure has been developed to measure fluoride concentration in bone biopsies by neutron activation analysis /NAA/. The NAA procedure is non-destructive so that the bone biopsies can be used subsequently for histological evaluation. The fluoride content is expressed as F/Ca ratio in the bone samples. The fluoride and calcium are measured using the reactions:¹⁹F/n, /²⁰F /t=11.2 s/ and⁴⁸Ca/n,/⁴⁹Ca/t=8.8 m/, respectively. The F/Ca ratio normalizes the fluoride to bone mineral avoiding the use of bone weight which is unreliable with fresh biopsy samples. This ratio also corrects for variations in neutron flux and gamma counting efficiencies. Results by this procedure were compared to biochemical determinations using an ion-selective electrode for fluoride and atomic absorption for calcium. The two methods gave results which agreed within ±5% which is the precision of the NNA procedure. The NAA method provides a simple and non-destructive procedure for fluoride measurement in bone biopsies for clinical studies. The method is now routinely used in our clinical studies for the fluoride measurements on biopsies from osteoporotic patients treated with fluoride therapy for nearly four years.     

Microprobe accessory for laser raman spectrometers

A Raman micro-focusing accessory has been designed for use with conventional laser Raman spectrometers and offers the advantage of allowing standard macro-Raman experiments to be done without removing the micro-focusing optics. Samples may be analysed with a spatial resolution adjustable to a limit of 1 μm. The viewing magnification can be varied without affecting the size of the laser focal spot. A thermocouple can be attached to the sample holder which may be flushed with cooled N₂ gas for increased sample stability. The usefulness of the Raman microprobe for the analysis of solid and fluid inclusions in geological samples is also demonstrated.     

Laser damage depths,carbon film thickness and possible zero metal enhancement in silver/pyridine sers: A scanning electron microscopy study

Surface-enhanced Raman scattering (SERS) by pyridine on anodized silver electrodes emanates from faint but visible carbon-overlayered regions within the laser damage microzone. Scanning electron microscopy reveals that initial silver surface damage consists of a central zone (0.03 mm diameter) of increased roughness surrounded by a halo (0.06 nm diameter) of intermediate roughness. Laser perforation studies on thin (500 nm) film electrodes reveal that the depth of laser damage under typical SERS conditions is ≈1250 silver-atom layers. Optical skin-depth measurements and surface tone comparisons indicate a carbon film depth of ≈300 layers. The implications for possible zero metal enhancement are considered.     

Control of a multisubunit DNA motor by a thermoresponsive polymer switch

The conjugation of thermoresponsive polymers to multisubunit, multifunctional hybrid type 1 DNA restriction-modification (R-M) enzymes enables temperature-controlled "switching" of DNA methylation by the conjugate. Polymers attached to the enzyme at a subunit distal to the methylation subunit allow retention of DNA recognition and ATPase activity while controlling methylation of plasmid DNA. This regulation of enzyme activity arises from the coil-globule phase transitions of the polymer as shown in light scattering and gel retardation assays.