[Simple method for the preparation of ketones of 4-hydroxycoumarin with the aid of phosphorus oxychloride].
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A systematic lab-scale experimental investigation is reported for the external nitrification (EN) biological nutrient removal (BNR) activated sludge (ENBNRAS) system, which is a combined fixed and suspended medium system. The ENBNRAS system was proposed to intensify the treatment capacity of BNR-activated sludge (BNRAS) systems by addressing two difficulties often encountered in practice: (a) the long sludge age for nitrification requirement; and (b) sludge bulking. In the ENBNRAS system, nitrification is transferred from the aerobic reactor in the suspended medium activated sludge system to a fixed medium nitrification system. Thus, the sludge age of the suspended medium activated sludge system can be reduced from 20 to 25 days to 8 to 10 days, resulting in a decrease in reactor volume per ML wastewater treated of about 30%. Furthermore, the aerobic mass fraction can also be reduced from 50% to 60% to <30% and concommitantly the anoxic mass fraction can be increased from 25% to 35% to >55% (if the anaerobic mass fraction is 15%), and thus complete denitrification in the anoxic reactors becomes possible. Research indicates that both the short sludge age and complete denitrification could ameliorate anoxic aerobic (AA) or low food/microorganism (F/M) ratio filamentous bulking, and hence reduce the surface area of secondary settling tanks or increase the treatment capacity of existing systems. The lab-scale experimental investigations indicate that the ENBNRAS system can obtain: (i) very good chemical oxygen demand (COD) removal, even with an aerobic mass fraction as low as 20%; (ii) high nitrogen removal, even for a wastewater with a high total kjeldahl nitrogen (TKN)/COD ratio, up to 0.14; (iii) adequate settling sludge (diluted sludge volume index [DSVI] <100 mL/g); and (iv) a significant reduction in oxygen demand.
Installing membranes for solid-liquid separation into biological nutrient removal (BNR) activated sludge (AS) systems makes a profound difference not only in the design of the BNR system itself, but also in the design approach for the whole wastewater treatment plant (WWTP). In multizone BNR systems with membranes in the aerobic reactor and fixed volumes for the anaerobic, anoxic, and aerobic zones (i.e., fixed volume fractions), the mass fractions can be controlled (within a range) with the interreactor recycle ratios. This zone mass fraction flexibility is a significant advantage in membrane BNR systems over conventional BNR systems with SSTs, because it allows for changing of the mass fractions to optimize biological N and P removal in conformity with influent wastewater characteristics and the effluent N and P concentrations required. For PWWF/ADWF ratios in the upper range (f(q) approximately 2.0), aerobic mass fractions in the lower range (f(maer) < 0.60), and high (usually raw) wastewater strengths, the indicated mode of operation of MBR BNR systems is as extended aeration WWTPs. Although the volume reduction compared with equivalent conventional BNR systems with secondary settling tanks is not as large (40% to 60%), the cost of the membranes can be offset against sludge thickening and stabilization costs. Moving from a flow-unbalanced raw wastewater system to a flow-balanced (f(q) = 1), low (usually settled) wastewater strength system can double the ADWF capacity of the biological reactor, but the design approach of the WWTP changes from extended aeration to include primary sludge stabilization. The cost of primary sludge treatment then has to be paid from the savings from the increased WWTP capacity.
The ability of bimetallic homo- and heteronuclear complexes of two spiro-linked ligands, viz. a biazacrown (i.e., 2,6,10,14,18,22-hexaazaspiro[11.11]tricosane (1)) and an azacrown-crown ether (i.e., 14,17,20,23,26-pentaoxa-2,6,10-triaza-spiro[11.15]heptacosane (2)), to promote the cleavage of the phosphoester linkage of dinucleoside 3',5'-phosphates and the phosphoric anhydride bridge of dinucleoside 5',5'-triphosphates was studied. In both reactions, the bimetallic homonuclear Cu2+ and Zn2+ complexes were better catalysts than their monometallic counterparts. The acceleration was two- to five-fold with the phosphoester cleavage and 3- to 20-fold with the phosphoric anhydride cleavage. Interestingly, the most-efficient catalyst of the phosphoester cleavage was the heterodinuclear Ni2+,Zn2+ complex of 1, the catalytic activity of which was up to 5- and 100-fold that of the homodinuclear Zn2+ and Ni2+ complexes, respectively. Moreover, this cooperative acceleration was observed to depend on the identity of the 5'-linked nucleoside: 3',5'-UpU and 3',5'-ApU were cleaved much faster than 3',5'-UpA, and no cooperative acceleration was observed with 3',5'-ApA. The reaction was second-order in hydroxide ion concentration, suggesting that a double deprotonation took place on going from the initial to the transition state. Evidently, in addition to deprotonation of the attacking 2'-OH group, N(3)H of the 5'-linked uridine was displaced by one of the metal ions of the cleaving agent. With the phosphoric anhydride cleavage, no similar cooperativity of two different metal ions was observed, but the greatest rate-acceleration was achieved with the homodinuclear Cu2+ complexes.
Reactions of [(eta5-C5H5)Ru(PR'3)2(Cl)] with NaBAr(F) [BAr(F)-=B{3,5-[C6H3(CF3)2]}4-; PR'3=PEt3 or 1/2Et2PCH2CH2PEt2) (depe)] and PR2H (R=Ph, a; tBu, b; Cy, c) in C6H5F, or of related cationic Ru(N2) complexes with PR2H in C6H5F, gave the secondary phosphine complexes [(eta5-C5H5)Ru(PR'3)2(PR2H)]+ BAr(F)- (PR'3=PEt3, 3 a-c; 1/2depe, 4 a,b) in 65-91 % yields. Additions of tBuOK (3 a, 4 a; [D6]acetone) or NaN(SiMe3)2 (3 b,c, 4 b; [D8]THF) gave the title complexes [(eta5-C5H5)Ru(PEt3)2(PR2)] (5 a-c) and [(eta5-C5H5)Ru(depe)(PR2)] (6 a,b) in high spectroscopic yields. These complexes were rapidly oxidized in air; with 5 a, [(eta5-C5H5)Ru(PEt3)2{P(=O)Ph2}] was isolated (>99 %). The reaction of 5 a and elemental selenium yielded [(eta5-C5H5)Ru(PEt3)2{P(=Se)Ph2}] (70 %); selenides from 5 c and 6 a were characterized in situ. Competitive deprotonation reactions showed that 5 a is more basic than the rhenium analog [(eta5-C5H5)Re(NO)(PPh3)(PPh2)], and that 6 b is more basic than PtBu3 and P(iPrNCH2CH2)3N. The latter is one of the most basic trivalent phosphorus compounds [pK(a)(acetonitrile) 33.6]. Complexes 5 a-c and 6 b are effective ligands for Pd(OAc)2-catalyzed Suzuki coupling reactions: 6 b gave a catalyst nearly as active as the benchmark organophosphine PtBu3; 5 a, with a less bulky and electron-rich PR2 moiety, gave a less active catalyst. The reaction of 5 a and [(eta3-C3H5)Pd(NCPh)2]+ BF4- gave the bridging phosphido complex [(eta5-C5H5)Ru(PEt3)2(PPh2)Pd(NCPh)(eta3-C3H5)]+ BAr(F)- in approximately 90 % purity. The crystal structure of 4 a is described, as well as substitution reactions of 3 b and 4 b.
BACKGROUND: Inefficient civil registration systems, non-report of deaths, variable standards in certifying death and the legal and social consequences of suicide are major obstacles in investigating suicide in the developing world. Very high rates of suicide have been recorded in the region in the general population and among younger people. OBJECTIVE: This paper describes the suicide rate among the elderly in Kaniyambadi block, Tamil Nadu, South India for the years 1994-2002 using verbal autopsies. METHOD: The setting for the study was a comprehensive community health program in a development block in rural South India. The main outcome measure was death by suicide diagnosed by a detailed verbal autopsy and census, birth and death data to identify the population base. RESULTS: The average annual suicide rate was 189 per 100,000 for people over 55 years of age. The ratio of male to female suicides was 1: 0.66. The age-specific suicide rate for men and women increased with age. Hanging (52%) and poisoning with organo-phosphorus compounds (39%) were the commonest methods employed for committing suicide. Significantly more women chose drowning or burning than men who preferred poisoning or hanging (chi2 19.75; df 1; p < 0.001). CONCLUSIONS: The suicide rate documented in this study among the elderly is very high. The reasons for the high suicide rate observed in older people are not known. There is a need to develop innovative strategies to reduce deaths by suicide.
Prior knowledge is required when quantifying in vivo (31)P magnetic resonance spectra from the brain or liver. The prior knowledge system we have used models both the phosphomonoester and phosphodiester resonances as two peaks of equal linewidth and fixed relative chemical shift. The analysis of the data is carried out in the time domain, which allows the broad component of the spectra to be modelled. This prior knowledge method has been tested for analysis of in vivo (31)P MR spectra from the liver and brain and gives results consistent with other methods that are also used to analyse the spectra, but with reduced variability. This technique may be utilized for studies requiring serial MR spectroscopy examinations, before and after patient treatment.
Landfills are sources of groundwater and soil pollution due to the production of leachate and its migration through refuse. This study was conducted in order to determine the extent of groundwater and soil pollution within and around the landfill of Seri Petaling located in the State of Selangor, Malaysia. The condition of nearby surface water was also determined. An electrical resistivity imaging survey was used to investigate the leachate production within the landfill. Groundwater geochemistry was carried out and chemical analysis of water samples was conducted upstream and downstream of the landfill. Surface water was also analyzed in order to determine its quality. Soil chemical analysis was performed on soil samples taken from different locations within and around the landfill in the vadose zone (unsaturated zone) and below the water table (in the soil saturated zone). The resistivity image along line L-L1 indicated the presence of large zones of decomposed waste bodies saturated with highly conducting leachate. Analysis of trace elements indicated their presence in very low concentrations and did not reflect any sign of heavy metal pollution of ground and surface water or of soil. Major ions represented by Na, K, and Cl were found in anomalous concentrations in the groundwater of the downstream bore hole, where they are 99.1%, 99.2%, and 99.4%, respectively, higher compared to the upstream bore hole. Electrical conductivity (EC) was also found in anomalous concentration downstream. Ca and Mg ions represent the water hardness (which is comparatively high downstream). There is a general trend of pollution towards the downstream area. Sulfates (SO4) and nitrates (NO3) are found in the area in low concentrations, even below the WHO standards for drinking water, but are significantly higher in the surface water compared to the groundwater. Phosphate (PO4) and nitrite (NO2), although present in low levels, are significantly higher at the downstream. There is no significant difference in the amount of fluoride (F) in the different locations. In the soil vadose zone, heavy metals were found to be in their typical normal ranges and within the background concentrations. Soil exchangeable bases were significantly higher in the soil saturated zone compared to the vadose zone, and no significant difference was obtained in the levels of inorganic pollutants. With the exception of Cd, the concentration ranges of all trace elements (Cu, Zn, Cr, Pb, and Ni) of Seri Petaling landfill soils were below the upper limits of baseline concentrations published from different sources.
The interaction of various lanthanide ions with vesicles of phosphatidylcholine from egg yolk has been followed by 31P NMR at 30 degrees C. From known magnetic properties of these ions, separation of the paramagnetic shift into a pure contact and a pseudo-contact part was carried out. Binding curves for the contact contribution (F curves) were obtained from vesicles in solutions of sodium salts with monovalent anions over a wide concentration range. These curves should be insensitive to any conformational effects due to ion binding. Indication of a conformational change in the lipid head group at low ion binding was obtained by studying the ratio between the contact and the pseudo-contact contributions. Besides the adsorption of lanthanide ions, specific anion binding to the surface was introduced to account for the enhanced chemical shifts (Cl- < Br- < NO3-). The results were analyzed in terms of the theory for the diffuse double layer (Gouy-Chapman-Grahame) with equilibrium conditions for the adsorbing cations and anions. Simulations of the titration curves furnished parameters for the ion-lipid interactions. The synergism between the cations and anions follows from the potential effects. Comparison of results with lanthanide ions and Ca2+ indicates that the anion adsorption probably depends on the nature of the adsorbed cation. Lanthanide ion binding to L-glycerophosphorylcholine is not influenced by sodium salts. The binding constant for this complex is weaker than with phosphatidylcholine. The chemical shifts for the lanthanide ion complexes with these two phosphorus compounds seem to be about the same.
The energy metabolites in rat brain in vivo were measured by using topical magnetic resonance (TMR) during the whole course of ischemia, in combination with the concomitant monitoring of electroencephalogram (EEG). Immediate loss of high energy phosphorus compounds, phosphocreatine (PCr) and ATP, resulted in the flattening of EEG after the induction of ischemia. PCr and ATP returned to almost normal level 30 min after recirculation of the ischemic brain, but EEG showed no recovery and the abnormality lasted for 12 h. The measurement of in vivo 31P-NMR is essential for the decision of the convalescence of cellular function in the brain.
Sorbitol-3-phosphate (S3P) and fructose-3-phosphate (F3P) are novel phosphorus compounds recently discovered and identified in the crystalline lens as well as other tissues. These phosphates increased with diabetes progression in streptozotocin-diabetic rat lenses. Treatment of these rats with an orally administered aldose reductase inhibitor eliminated S3P and intramuscularly injected insulin obliterated F3P. These results indicate that enzymes catalyzing S3P and F3P formation co-activate with aldose reductase activation and hyperglycemia, respectively.
Energy dispersive X-ray microanalysis is a powerful tool that can reveal the presence and relative quantities of elements in minute particles in biologic materials. Although this technique has been used in some aspects of dental research, it has rarely been applied to diagnostic oral pathology. The purpose of this paper is to inform practicing dentists and oral specialists about the diagnostic potential of this procedure by presenting three case reports. The first case involved the identification of flakes of a metallic material claimed by a 14-year-old girl to appear periodically between her mandibular molars. In the second case, a periodontist was spared a lawsuit when a freely mobile mass in the antrum of his patient was found to be a calcium-phosphorus compound not related to the periodontal packing that had been used. The third case involved the differential diagnosis of amalgam tattoo and graphite tattoo in a pigmented lesion of the hard palate mucosa. The results of the analyses were significant and indicate a role for this technique in the assessment of selected cases. Potential for wider use of energy dispersive X-ray microanalysis in diagnostic oral pathology exists as research progresses.
Thirty-five patients each with a tentative diagnosis of osteomyelitis of the mandible were examined with 99Tcm-labeled phosphorus compounds. The scintigraphic findings were compared with the radiographic features and related to disease stages to evaluate the diagnostic potential of bone scintigraphy in different disease stages. The scintigraphy was valuable to exclude bone tissue involvement in some patients with clinical signs and symptoms similar to those of osteomyelitis and with equivocal radiographic findings. In 13 patients with chronic osteomyelitis, scintigraphy revealed a larger extent of the lesion than the radiography. In lesions with permeated bone destructions with penetration of the cortex, the uptake of 99Tcm was higher than in lesions with a motheaten or sclerotic appearance. This study supports the view that 99Tcm-bone scintigraphy is a useful tool at various stages of osteomyelitis, that is, in its early detection, in the treatment or biopsy planning, and in the evaluation of the efficacy of treatment.
OBJECTIVES: The objective of this study was to characterize the influence of various metals, metal compounds, and P2O5 as a nucleating agent on the color and translucency of a Li2O-Al2O3-CaO-SiO2 glass-ceramic. METHODS: Glass frits of Li2O-Al2O3-CaO-SiO2 (LACS), LACS with 1 mol% P2O5 (LACSP), and/or LACS with one of 16 colorants were melted, poured into a cylindrical graphite mold, cut into disks, annealed, nucleated, crystallized, and annealed again. Ten translucency measurements of each of five disks were made using a tristimulus colorimeter and a D65 standard CIE illuminant. The color of each disk was analyzed using the CIE L*a*b* color space system (1976) as a function of colorant, colorant concentration, and P2O5. RESULTS: Mean L* values of glass-ceramic disks ranged from 63.5 for LACS containing 6.2 mmol% FeCl3 (LACSP-6.2Fe) to 84.1 for LACS. No significant difference (p > 0.05) was found between the mean L* values for LACS, LACSP, and LACS with 0.19 mmol% AgNO3 (LACS-0.19Ag). The mean contrast ratio of glass-ceramic specimens ranged from 0.42 (LACS and LACS-1.0Fe) to 0.98 (LACS-0.78Ag). Mean color difference values varied from 5.8 (LACSP-1.0Fe vs. LACS) to 36.3 (LACSP-0.78Ag vs. LACSP). SIGNIFICANCE: The results of this study indicate that, because certain colorants in glass-ceramics affect opacity as well as hue and chroma, the development of glass-ceramics should be simplified by: 1) employing a nucleating agent that does not affect hue or chroma significantly, 2) controlling fixed levels of translucency consistent with mechanical and physical property requirements, and 3) varying the hue and chroma by means of colorants that do not affect the crystallization process. This implies that the volume fraction and mean size of crystals must be controlled, since the translucency or opacity of glass-ceramics is associated with scattering of light at the interfaces between adjacent crystals, and between crystals and the glass phase because of differences in refractive indices (McMillan, 1979a).
Methylphosphonate in conjunction with 31P-NMR spectroscopy was used for the measurement of transmembrane delta pH in human erythrocytes stored at 4 degrees C for up to 5 weeks in a nutrient medium. Intra- and extracellular pH was determined using calibration curves based on the pH-dependent separation between the NMR resonances of methylphosphonate and orthophosphate (Pi). A comprehensive statistical procedure is presented for the determination of the variance of NMR-based pH estimates. The entry of methylphosphonate into erythrocytes was more rapid at low pH and uptake was fully inhibited by the band 3 reagent, disodium 4,4-diisothiocyano-2,2'-disulphonic acid stilbene. The distribution ratio of methylphosphonate concentration inside and outside the cells was used to calculate the membrane potential; the analysis depends on a consideration of the Donnan equilibrium for an anion with one or two charges. Furthermore, the analysis does not depend on the pH estimates but relies solely on concentration estimates. The chemical shift of methylphosphonate was not subject to the variations associated with specific intracellular binding encountered with many other phosphorus compounds, including Pi. On the other hand, the ionic strength dependence of the chemical shift of methylphosphonate, contrary to earlier reports, is comparable in magnitude (but opposite in sign) to that of Pi.