"A review of: “High Resolution Spectroscopy by J. Michael Hollas Butteworths; Boston 638 Pages + xv Price: $115.00”." Spectroscopy Letters, 15(12), p. 1017

Twenty-five samples of soft plaque and calcified plaque deposits from human hearts or aorta were analyzed using inductively coupled plasma-mass spectrometry (ICP-MS). The determined elements were Ca, P, Na, K, Mg, Zn, Cu, Ba, Pb, Fe, Al, Si, and S. Results showed that the concentration of all elements in the soft plaque was at the micromolar level. In the calcified deposits, the concentrations of Ca and P were at least an order of magnitude higher than the soft plaque, but the other elements were at the same order of magnitude. In the calcified plaque the molar ratios of Ca/P suggested that a significant portion existed as hydroxyapatite Ca10(PO4)6(OH)3. However, their absolute concentrations indicated that this compound was not a major component of the plaque although it may play a major role in determining the crystal structure of the deposit. In some samples the Ca/P ratio was too high to conform to hydroxyapatite. In others it was too low. This indicated that both the calcium and phosphorus existed in other chemical forms which varied from sample to sample. In the soft tissue the P level was high indicating it existed primarily in chemical forms other than hydroxyapatite. The presence of homocysteine is often associated with heart disease. However, the low levels of sulfur indicate that although it may be present, it is not a major component of the plaque, but may nevertheless play an important role in its formation.

The plaque deposits in bypass arteries and native arteries from the same heart have been studied using solid state cross polarization nuclear magnetic resonance (CP/MAS NMR). Both 13 C and 31 P signals were observed. The samples are of interest because plaque in native arteries may have deposited during the lifetime of the patient. However, plaque in the bypass occurred since bypass surgery. It has been observed that the mature plaque in native arteries was more calcified than that in bypass arteries, especially if the latter had not matured to become significant in size. Results showed that the concentrations of carboxylate carbons present in cholesterol esters were similar in native and bypass arteries. However, the areas of the 13 C peaks of the carboxylate compared to the sum of areas of all other 13 C arteries indicated that the carboxylate was attached to five or six other carbons. From this we can calculate that the carboxylate to other carbon ratio in the remainder must be 1:4 or 1:3. This indicates large quantities of other organic compounds in the deposits. Studies of 31 P showed that phosphorus existed primarily as hydroxyapatite in the crystalline native plaque. However, a large proportion existed as organic phosphorus in the bypass plaque. In addition, we studied the interactions of calcium with homocysteine and cholesterol. Calcium-homocysteine and cholesterol-homocysteine precipitates were characterized using 13 C solid state NMR. Results showed that calcium appeared to interact with sulphur in the homocysteine which seemed to form dimers and polymers.

As part of an ongoing study on atherosclerotic arteries, the concentrations of 12 elements in a native and by-pass human coronary artery plaque deposits from five human hearts were determined using inductively coupled Plasma-mass spectrometry (ICP-MS). These elements were Ca, P, Na, K, Mg, Zn, Cu, Ph, Fe, Al, Si, and S. For Zn, Ca, Ph, Fe, Al, and Si, the levels were at the fractional pmol/g levels and they probably played an unimportant role in plaque development. Sulfur levels varied from 23 to 140 mumols indicative of the possible presence of homocysteine, but there appeared to be no consistent relationship between by-pass and native concentrations. The calcium and phosphorus concentrations were relatively high in all cases, but the ratio of their molecular concentrations did not correspond to hydroxyapatite, which is conventionally considered to be the chemical form of calcium in heart plaque. In the mature native plaque, high calcium/phosphorus ratios indicated calcium in chemical forms other than hydroxyapatite. In undeveloped by-pass plaque, the phosphorus concentration was too high to be as hydroxyapatite but may be phospholipids. Because it is difficult to get suitable samples, only five heart samples were available. Therefore, these results should be treated as preliminary.

The use of a Thermospray (TSP) in flame atomic absorption (FAA) increases sensitivity. Experimental data showed that a 75 mu m orifice and 0.05 cm 1D capillary produced a sensitivity increase of about 10(4) compared to commercial flame atomizer. The signal was independent of power input over a considerable power range.Based on this data a TSP nebulizer was built and used for interfacing HPLC and FAA. The instrument was used for cadmium speciation studies on urine. The presence of numerous cadmium compounds was revealed.With further modification on TSP construction design, even higher analytical sensitivity for ultra trace metal analysis and better compatibility for interfacing HPLC with MS, ICP-MS, FAAS, and ICP-AES can be expected.

Metalothionein complexes divalent metals such as cadmium and thereby assists in removing Cd2+ from the bloodstream. It has been stated that excess Zn2+ in the blood stream will displace Cd2+ from the Cd metalothionein complex and release Cd2+ back into the bloodstream. This was an in vitro study to study this reaction.A metal speciation technique was utilized with a newly developed analytical thermospray nebulizer(TSP) interfaced '' high-speed high performance liquid chromatography (HPLC)'' with flame atomic absorption spectroscopy (FAAS). The in vitro synthesis of human biological conditions in the experimental procedures allowed the mole ratio at which the replacement reaction being initiated Lo be determined as 1:100:1,000 mol ratio of zinc:cadmium:metalothioaein. This corresponded to actual concentration ratios of 0.015:1.0:40.0 ppm, respectively.

Early work on cadmium speciation of body fluids using GC-AA indicated the presence of CdCl2, but other non-volatile Cd compounds were not detected (1). Such compounds may be detected by LC-AA.To this end, an HPLC-Flame AA system (FAAS) has been developed using a thermospray. This device greatly increased the sensitivity of the flame CFA system. Its use revealed the presence of numerous non-volatile cadmium compounds in urine and perspiration and confirmed our earlier observation that perspiration is a major process for removing cadmium from the body. Using data obtained, the half life of cadmium in the body is about 18 months rather than 20-30 years as currently believed.

These studies showed that aluminum in water at acidities below pH 4.5 was taken up by fish and accumulated preferentially in the gills. This led to the rapid death of the fish. The toxicity of the aluminum was decreased at higher pH. Also certain ions, particularly Fe3+ and PO43- decreased the aluminum toxicity even at pH 4.5. However the presence of Ca++ of Mg++ did not modify the aluminum toxicity indicating that liming has little positive effect other than altering the pH of the water.

A study was carried out to find out if leaf extracts from different plants could be used to reduce the toxic effects of aluminum on fish. The types of leaves were pine, oak, sweet gum, willow, alligator grass, pecan and pine. Shiners (Notropis) fish were used for the study.The results obtained showed that if the pH was controlled to pH 4.5 the presence of leaf extracts did not mitigate the toxic effect of aluminum. However at pH 5 and above the presence of leaf extracts reduced aluminum toxicity to fish.When dried leaf extract was added to aluminum solution at pH 4.5 the final pH increased to 6.2 depending on the type of leaves. With no adjustment back to pH 4.5 the toxic effect of aluminum was greatly reduced except when pine or oak were used.1. The presence of humic and fulvic acids in the leaf extracts were ascertained by the ratio of their absorbances at 465 nm and 665 nm. The results indicated that the presence of humic or fulvic acids depended on type of leaves and the length of time the leaves were soaked in water. Longer soaking resulted in increased formation of humic acid while shorter soaking resulted mostly in the formation of fulvic acids. Pine leaves showed very little tendency to form fulvic or humic acid even after soaking for a year.Fluorescence studies obtained showed that there was an increased in the intensity of fluorescence and a shift in the shorter wavelength upon addition of aluminum to leaf extracts indicating a chemical reaction. The wavelength of the emission maxima corresponded to that of humic and fulvic acids.

Patients who have undergone bypass surgery often find the bypasses fill up again with plaque ("new plaque") whereas the heart arteries not bypassed contain plaque deposited since childhood ("old plaque"). A preliminary study was undertaken to characterize and contrast the chemical compositions of these "new" and 'old" plaques.The samples were obtained from a particular surgeon, His patients had had bypass surgery but the bypasses had refilled over a period of a few years. In the surgery both bypassed and non-bypassed arteries were reopened as necessary to improve circulation by surgically drilling out some plaque. This plaque was analyzed.Each particular sample was divided into two portions. One portion was used for lipid analysis using High Pressure Liquid Chromatography (HPLC) and Thin Layer Chromatography (TLC) while the other portion was used for the determination of selected metals using Inductively Coupled Plasma (ICP). The results are summarized below. 1. The analytical procedures (HPLC and ICP) were fast and reliable techniques for plaque characterization and provided extensive information. 2. Phospholipids, lipids, and triglycerides were found in the plaque but the types of phospholipids, lipids and triglycerides varied from one patient to the next. 3. Cholesterol and/or cholesterol esters such as oleate, linoleate and arachidonate were found in both old and newly deposited plaque but not all samples contained cholesterol. 4. The results of metal analyses indicated there was increased deposition of Cu, Zn, Mn, Ca, Mg and P in the newly deposited plaque compared to the old plaque, but Na, Cr, Fe and K decreased in concentration in the new material. 5. The concentrations of calcium and phosphorus were almost sixteen times higher in the new plaque compared to the old deposits. 6. Ca/Mg and Ca/Na ratios was much higher in the new material than the old plaque and the ratio in both the old and the new was much higher than in normal blood. For example the average Ca/Mg ratio in the new plaque was found to be about 77/1 while in the old plaque it was found to be 28/1 in matched samples. The normal ratio in the blood plasma is around 3/1. 7. The Cu/Zn ratios were less than 1/1 in all samples. The ratio in the new material was lower than in the old. 8. Results suggest a change in body metabolism in later life leading to the formation of a different plaque from that deposited in earlier life.

Journal of the Chinese Chemical SocietyVolume 37, Issue 4 p. 313-319 Article Advances in Atomice Absorption and Plasma Emission Spectrography J.W. Robinson, J.W. Robinson Department of Chemistry Louisiana State University Baton Rouge, LA 70803 U.S.A.Search for more papers by this author J.W. Robinson, J.W. Robinson Department of Chemistry Louisiana State University Baton Rouge, LA 70803 U.S.A.Search for more papers by this author First published: August 1990 https://doi.org/10.1002/jccs.199000043Citations: 1AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Citing Literature Volume37, Issue4August 1990Pages 313-319 RelatedInformation

Thermospray nebulizer interfaced HPLC-Flame AAS was used to study the effect of heavy metals (Al, Cd, Cu, Hg and Zn) on the chlorophylls of duckweed. Flame AAS was used as a metal specific detector of HPLC. Study indicated that heavy metals promote the degradation of chlorophylls. No evidence of direct replacement of central magnesium with heavy metals was found.

Studies indicated that duckweed absorbed mercury in water (e.g. lakes) strongly and that after three days it contained up to 2000 ppm of mercury by weight of duckweed. The uptake of mercury was little affected by acidity at pH 4.0 and pH 5.0. The presence of copper ion suppressed the mercury uptake significantly. The presence of 1.0 mM EDTA in solution also suppressed the mercury uptake significantly. Further 10 mg of humic acid in 400 mL solution suppressed the mercury uptake to some degree, probably by complexing the mercury.

A circular flame atomizer system using a quartz T flame adapator has been developed for the direct determination of mercury. A thermospray nebulizer was used as a sample introduction device to the atomizer. This design gave a sensitivity (1% absorption) of 0.20 ppm and detection limits of 10 ppb at 1.0 mL/min solvent flow at 253.7 nm. The absolute sensitivity was 25 ng and absolute detection limits was 1.5 ng.