Synthesis and vibrational spectroscopy of halotrichite and bilinite

Near infrared (NIR), infrared (IR) spectroscopy and X-ray diffraction (XRD) have been applied to halotrichites of the formula FeAl2(SO4)4∙22H2O and Fe2+Fe23+(SO4)4∙22H2O. Comparison of the halotrichites and their starting materials has been used to give a better understanding of the bonding involved in these types of minerals. The vibrational spectroscopy data has shown that Fe2+ oxidises during the formation of halotrichite, no preventative measures were implemented to prevent oxidation, and this has been clearly shown by the position and broadness of electronic bands of transition metals in the NIR spectra (12500 to 7500 cm-1). It is apparent from this region that Fe3+ substitutes for Al3+ in the synthesis of halotrichite. Due to the oxidation of Fe2+ to Fe3+ the halotrichite sample contains a small portion of bilinite. This has been confirmed by XRD, peaks at 9 and 14° 2θ were observed in the halotrichite sample and are identical to the XRD pattern obtained for bilinite. Substitution of aluminium for Fe3+ has resulted in significant changes in the overall infrared and NIR spectral profiles. However, the lower wavenumber regions of the NIR spectra have very similar spectral profiles, which indicate a similar structure to halotrichite has formed for bilinite. This work has shown that iron halotrichites can be synthesised and characterised by infrared and NIR spectroscopy.

Synthesis of proteoglycan 4 by chondrocyte subpopulations in cartilage explants, monolayer cultures, and resurfaced cartilage cultures

Objective: To quantify the levels of proteoglycan 4 (PRG4) expression by subpopulations of chondrocytes from superficial, middle, and deep layers of normal bovine calf cartilage in various culture systems. Methods: Bovine calf articular cartilage discs or isolated cells were used in I of 3 systems of chondrocyte culture: explant, monolayer, or transplant, for 1-9 days. PRG4 expression was quantified by enzyme-linked immunosorbent assay of spent medium and localized by immunohistochemistry at the articular surface and within chondrocytes in explants and cultured cells. Results: Superficial chondrocytes secreted much more PRG4 than did middle and deep chondrocytes in all cultures. The pattern of PRG4 secretion into superficial culture medium varied with the duration of culture, decreasing with time in explant culture (from similar to25 mug/cm(2)/day on days 0-1 to similar to3 mug/cm(2)/day on days 5-9), while increasing in monolayer culture (from similar to1 pg/cell/day on days 0-1 to similar to7 pg/cell/day on days 7-9) and tending to increase in transplant culture (reaching similar to2 mug/cm(2)/day by days 7-9). In all of the culture systems, inclusion of ascorbic acid stimulated PRG4 secretion, and the source of PRG4 was immunolocalized to superficial cells. Conclusion: The results described here indicate that the phenotype of PRG4 secretion by chondrocytes in culture is generally maintained, in that PRG4 is expressed to a much greater degree by chondrocytes from the superficial zone than by those from the middle and deep zones. The marked up-regulation of PRG4 synthesis by ascorbic acid may have implications for cartilage homeostasis and prevention of osteoarthritic disease. Transplanting specialized cells that secrete PRG4 to a surface may impart functional lubrication and be generally applicable to many tissues in the body.

Synthesis and Raman spectroscopic characterisation of hydrotalcites based on the formula Ca6Al2(CO3)(OH)16· 4H2O

We have successfully synthesized hydrotalcites (HTs) contg. calcium, which are naturally occurring minerals. Insight into the unique structure of HTs has been obtained using a combination of X-ray diffraction (XRD) as well as IR and Raman spectroscopies. Calcium-contg. hydrotalcites (Ca-HTs) of the formula Ca4Al2(CO3)(OH)12·4H2O (2:1 Ca-HT) to Ca8Al2(CO3)(OH)20· 4H2O (4:1 Ca-HT) have been successfully synthesized and characterised by XRD and Raman spectroscopy. XRD has shown that 3:1 calcium HTs have the largest interlayer distance. Raman spectroscopy complemented with selected IR data has been used to characterize the synthesized Ca-HTs. The Raman bands obsd. at around 1086 and 1077 cm-1 were attributed to the ν1 sym. stretching modes of the (CO32-) units of calcite and carbonate intercalated into the HT interlayer. The corresponding ν3 CO32- antisym. stretching modes are found at around 1410 and 1475 cm-1.

The effect of synthesis temperature on the formation of hydrotalcites in Bayer liquor : a vibrational spectroscopic analysis

The seawater neutralisation process is currently used in the Alumina industry to reduce the pH and dissolved metal concentrations in bauxite refinery residues, through the precipitation of Mg, Al, and Ca hydroxide and carbonate minerals. This neutralisation method is very similar to the co-precipitation method used to synthesise hydrotalcite (Mg6Al2(OH)16CO3•4H2O). This study looks at the effect of temperature on the type of precipitates that form from the seawater neutralisation process of Bayer liquor. The Bayer precipitates have been characterised by a variety of techniques, including X-ray diffraction, Raman spectroscopy and infrared spectroscopy. The mineralogical composition of Bayer precipitates largely includes hydrotalcite, hydromagnesite, and calcium carbonate species. XRD determined that Bayer hydrotalcites that are synthesised at 55 °C have a larger interlayer distance, indicating more anions are removed from Bayer liquor. Vibrational spectroscopic techniques have identified an increase in hydrogen bond strength for precipitates formed at 55 °C, suggesting the formation of a more stable Bayer hydrotalcite. Raman spectroscopy identified the intercalation of sulfate and carbonate anions into Bayer hydrotalcites using these synthesis conditions.