Pharmacognostical and phytochemical studies on Origanum vulgare L.(Laminaceae).

With increasing demand in the field of herbal medicines and cosmetics, it has become necessary and pertinent to probe into the area of systematic knowledge about herbal drugs. There is a need for the application of this knowledge in authentification, detailed study and practical utilization of crude drugs. The present paper deals with the taxonomy, anatomy, powder study pertaining to organoleptic, microscopic, fluorescence, physical constant evaluations and phytochemical screening of Origanum vulgare L.

Retention studies on uranium, thorium and lanthanides with amide modified reverse phase support and its applications.

The retention behaviour of uranium and thorium was investigated on modified reverse phase supports using 3-oxo-pentanedioicacid bis-[bis-(2-ethyl-hexyl)-amide (OPAEHA), 3-oxo-pentanedioicacid bis diisobutyl amide (OPAIBA) and bis-2-ethylhexyl succinamic acid (BEHSA). alpha-Hydroxy isobutyric acid (alpha-HIBA) was employed as the complexing reagent for elution. Elution profiles of uranium and thorium were studied as a function of the modifier concentration, mobile phase composition and its pH. Based on these investigations, a novel high performance liquid chromatography (HPLC) based separation technique was developed using BEHSA modified support for the isolation and quantitative determination of lanthanides as a group in uranium matrix. Hundreds of samples obtained from pyrochemical reprocessing of molten salts containing lanthanides in uranium matrix (e.g. 1:20,000) were separated and determined within 7 min using the coated support. The advantage of the present HPLC technique lies in the simultaneous separation and assay of total lanthanides and uranium whereas other analytical methods necessitate the separation of uranium matrix prior to lanthanide assay.

Sequential separation of lanthanides, thorium and uranium using novel solid phase extraction method from high acidic nuclear wastes.

A novel grafted polymer for selective extraction and sequential separation of lanthanides, thorium and uranium from high acidic wastes has been developed by grafting Merrifield chloromethylated (MCM) resin with octyl(phenyl)-N,N-diisobutylcarbamoyl-methylphosphine oxide (CMPO) (MCM-CMPO). The grafting process is well characterized using FT-IR spectroscopy, (31)P and (13)C CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNPS elemental analysis. The influence of various physico-chemical parameters during metal ion extraction by the resin phase are studied and optimized by both static and dynamic methods. The resin shows very high sorption capacity values of 0.960mmolg(-1) for U(VI), 0.984mmolg(-1) for Th(IV), 0.488mmolg(-1) for La(III) and 0.502mmolg(-1) for Nd(III) under optimum HNO(3) medium, respectively. The grafted polymer shows faster rate exchange kinetics (<5min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, sequential separation of the analytes is possible with varying eluting agents. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. All the analytical data is based on triplicate analysis and measurements are within 3.5% rsd reflecting the reproducibility and reliability of the developed method.

High performance liquid chromatographic studies on lanthanides, uranium and thorium on amide modified reversed phase supports.

The retention behavior of uranium, thorium and lanthanides has been investigated with amide modified reversed phase C(18) supports using alpha-hydroxy isobutyric acid (alpha-HIBA) as the mobile phase. Four structurally different amide moieties namely, 4-hydroxy-N,N-dihexyl butyramide (4HHBA), 4-hydroxy-N,N-di-2-ethylhexylhexanamide (4HEHHA), bis(N,N,N',N'-2-ethylhexyl)malonamide (B2EHM) and N-methyl-tris(dihexylcarbamoyl-3-methoxy)pivolamide (MTDCMPA) have been synthesized and studied. Among the various amide coated columns, the supports modified with 4HHBA, B2EHM and MTDCMPA exhibit an interesting retention for uranium and thorium, which is different from 4HEHHA modified support. The retention time for uranium and thorium increases with increasing amide concentration for 4HHBA, B2EHM and MTDCMPA supports, while the same decreases with increasing 4HEHHA content. However, the separation factor for uranium and thorium is greater on a 4HEHHA support, compared to an unmodified C(18) column, reflecting the amide's preferential complexation of uranium over thorium. Columns modified with 4HHBA, B2EHM and MTDCMPA exhibit relatively higher retentions for lanthanides. However, MTDCMPA modified support shows a different elution profile for lanthanides compared to 4HHBA, and B2EHM modified columns. Individual separations of heavier lanthanides, i.e., from gadolinium to lutetium also have been achieved using 4HHBA and B2EHM modified supports. The influence of modifier content, mobile phase concentration and its pH on the retention of metal ions has also been studied. Based on these investigations, an efficient high performance liquid chromatographic method (HPLC) has been developed for the rapid separation of uranium from thorium as well as for the individual separation of heavier lanthanides.

A study of the extraction behavior of thallium with tribenzylamine as the extractant.

A simple solvent extraction study for thallium has been conducted based on the extraction of thallium as a chlorocomplex (tetrachlorothallate (III) anion) with tribenzylamine. Radiolabelled Tl (III) was used to study the extraction behavior of thallium. The beta activity of the extracted ion-association complex has been monitored using liquid scintillation counting and Geiger Muller counter. The effect of various diluents such as toluene, chloroform and isobutylmethylketone (MIBK) were studied. The extraction efficiency was 95% when chloroform and MIBK were used as diluents for tribenzylamine at an overall concentration of 0.25 mol dm(-3) NaCl and 0.5 mol dm(-3) H(2)SO(4). The phenomenon of severe chemical quenching was observed with chloroform as the diluent. The recovery of thallium was found to be 95% at varying concentrations ranging from 5 to 20 microg ml(-1) Tl (III) with a relative standard deviation of 2.5%.

Selective extraction of U(VI) over Th(IV) from acidic streams using di-bis(2-ethylhexyl) malonamide anchored chloromethylated polymeric matrix.

A new chelating polymeric sorbent has been developed using Merrifield chloromethylated resin anchored with di-bis (2-ethylhexyl) malonamide (DB2EHM). The modified resin was characterized by (13 )C CPMAS NMR spectroscopy, FT-NIR-FIR spectroscopy, CHN elemental analysis and also by thermo gravimetric analysis. The fabricated sorbent showed superior binding affinity for U(VI) over Th(IV) and other diverse ions, even under high acidities. Various physio-chemical parameters, like solution acidity, phase exchange kinetics, metal sorption capacity, electrolyte tolerance studies, etc., influencing the resin's metal extractive behavior were studied by both static and dynamic method. Batch extraction studies performed over a wide range of solution acidity (0.01-10M) revealed that selective extraction of U(VI) could be achieved even up to 4M acidity with distribution ratios (D) in the order of approximately 10(3). The phase exchange kinetics studies performed for U(VI) and Th(IV) revealed that time duration of <15min was sufficient for >99.5% extraction. But similar studies when preformed for trivalent lanthanides gave very low D values (<50), with the extraction time extending up to 60min. The metal sorption studies performed for U(VI) and Th(IV) at 5M HNO(3) was found to be 62.5 and 38.2mgg(-1),respectively. Extraction efficiency in the presence of inferring electrolyte species and inorganic cations were also examined. Metal ion desorption was effective using 10-15mL of 1M (NH(4))(2)CO(3) or 0.5M alpha-hydroxy isobutyric acid (HIBA). Extraction studies performed on a chromatographic column at 5M acidity were found to give enrichment factor values of 310 and 250 for U(VI) and Th(IV), respectively. The practical utility of the fabricated chelating sorbent and its efficiency to extract actinides from acidic waste streams was tested using a synthetic nuclear spent fuel solution. The R.S.D. values obtained on triplicate measurements (n = 3) were within 5.2%.

Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer.

A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using (13)C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physio-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42mmolg(-1) for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6M HNO(3) medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t(1/2) values of <6min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30mugL(-1). Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100mL of distilled water (for actinides) followed by elution with 20mL of 0.1M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.

DAPPA grafted polymer: an efficient solid phase extractant for U(VI), Th(IV) and La(III) from acidic waste streams and environmental samples.

A new class of polymeric resin has been synthesized by grafting Merrifield chloromethylated resin with (dimethyl amino-phosphono-methyl)-phosphonic acid (MCM-DAPPA), for the preconcentration of U(VI), Th(IV) and La(III) from both acidic wastes and environmental samples. The various chemical modification steps involved during grafting process are characterized by FT-IR spectroscopy, (31)P and (13)C-CPMAS (cross-polarized magic angle spin) NMR spectroscopy and CHNS/O elemental analysis. The water regain capacity data for the grafted polymer are obtained from thermo-gravimetric (TG) analysis. The influence of various physico-chemical parameters during the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The significant feature of this grafted polymer is its ability to extract both actinides and lanthanides from high-level acidities as well as from near neutral conditions. The resin shows very high sorption capacity values of 2.02, 0.89 and 0.54mmolg(-1) for U(VI), 1.98, 0.63 and 0.42mmolg(-1) for Th(IV) and 1.22, 0.39 and 0.39mmolg(-1) for La(III) under optimum pH, HNO(3) and HCl concentration, respectively. The grafted polymer shows faster phase exchange kinetics (<5min is sufficient for 50% extraction) and greater preconcentration ability, with reusability exceeding 20 cycles. During desorption process, all the analyte ions are quantitatively eluted from the resin phase with >99.5% recovery using 1M (NH(4))(2)CO(3), as eluent. The developed grafted resin has been successfully applied in extracting Th(IV) from high matrix monazite sand, U(VI) from sea water and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.9% R.S.D. reflecting the reproducibility and reliability of the developed method.

Extraction of U(VI), Th(IV), and La(III) from acidic streams and geological samples using AXAD-16-POPDE polymer.

A new chromatographic extraction method has been developed using Amberlite XAD-16 (AXAD-16) resin chemically modified with (3-hydroxyphosphinoyl-2-oxo-propyl)phosphonic acid dibenzyl ester (POPDE). The chemically modified polymer was characterized by 13C CPMAS and 31P solid-state NMR, Fourier Transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis. Extraction studies performed for U(VI), Th(IV), and La(III) showed good distribution ratio ( D) values of approximately 10(3), even under high acidities (1-4 M). Various physiochemical parameters that influence the quantitative metal ion extraction were optimized by static and dynamic methods. Data obtained from kinetic studies revealed that a time duration of < or =10 min was sufficient to achieve complete metal ion extraction. Maximum metal sorption capacity values under optimum pH conditions were found to be 1.38, 1.33, and 0.75 mmol g(-1) for U(VI), Th(IV), and La(III), respectively. Interference studies performed in the presence of concentrated diverse ions and electrolyte species showed quantitative analyte recovery with lower limits of analyte detection being 10 and 20 ng cm(-3) for U(VI) and both Th(IV) and La(III), respectively. Sample breakthrough studies performed on the extraction column showed an enrichment factor value of 330 for U(VI) and 270 for Th(IV) and La(III), respectively. Analyte desorption was effective using 15 cm3 of 1 M (NH4)2CO3 with >99.8% analyte recovery. The analytical applicability of the developed resin was tested with synthetic mixtures mimicking nuclear spent fuels, seawater compositions and real water and geological samples. The rsd values of the data obtained were within 5.2%, thereby reflecting the reliability of the developed method.

Selective extraction of U(VI), Th(IV), and La(III) from acidic matrix solutions and environmental samples using chemically modified Amberlite XAD-16 resin.

A new grafted polymer has been developed by the chemical modification of Amberlite XAD-16 (AXAD-16) polymeric matrix with [(2-dihydroxyarsinoylphenylamino)methyl]phosphonic acid (AXAD-16-AsP). The modified polymer was characterized by a combination of (13)C CPMAS and (31)P solid-state NMR, Fourier transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis (TGA). The distribution studies for the extraction of U(VI), Th(IV), and La(III) from acidic solutions were performed using an AXAD-16-AsP-packed chromatographic column. The influences of various physiochemical parameters on analyte recovery were optimized by both static and dynamic methods. Accordingly, even under high acidities (>4 M), good distribution ratio (D) values (10(2)-10(4)) were achieved for all the analytes. Metal ion desorption was effective using 1 mol L(-1) (NH(4))(2)CO(3). From kinetic studies, a time duration of <15 min was sufficient for complete metal ion saturation of the resin phase. The maximum metal sorption capacities were found to be 0.25, 0.13, and 1.49 mmol g(-1) for U(VI); 0.47, 0.39, and 1.40 mmol g(-1) for Th(IV); and 1.44, 1.48, and 1.12 mmol g(-1) for La(III), in the presence of 2 mol L(-1) HNO(3), 2 mol L(-1) HCl, and under pH conditions, respectively. The analyte selectivity of the grafted polymer was tested in terms of interfering species tolerance studies. The system showed an enrichment factor of 365, 300, and 270 for U(VI), Th(IV), and La(III), and the limit of analyte detection was in the range of 18-23 ng mL(-1). The practical applicability of the polymer was tested with synthetic nuclear spent fuel and seawater mixtures, natural water, and geological samples. The RSD of the total analytical procedure was within 4.9%, thus confirming the reliability of the developed method.

Selective enrichment of U(VI), Th(IV) and La(III) from high acidic streams using a new chelating ion-exchange polymeric matrix.

An off-line extraction chromatographic technique has been developed using Amberlite XAD-16 (AXAD-16)-N,N-dihexylcarbamoylmethyl phosphonic acid, as the stationary phase for the extraction of uranium, thorium and lanthanum from nuclear spent fuels as well as from geological and natural water resources. The chemical modifications of the polymeric matrix were monitored using FT-IR spectroscopy, CHNPS elemental analysis and also by thermo gravimetric analysis for water regain measurements. Various physio-chemical parameters influencing the quantitative metal ion extraction by the resin phase were optimized by both static and dynamic methods. The developed resin matrix showed good distribution ratio values under wide concentrations of acidity and pH conditions. Moreover, the sequential separation of analytes is also possible at sample pH 6.5. Also, the polymeric matrix showed superior metal sorption capacities and rapid metal exchange kinetics with a high sample flow rate value of 26cm(3)min(-1) for all the three analytes. Thus, reducing the time of analyte extraction from large number of samples anticipated in nuclear waste management programs. The quantitative metal ion recovery of >99.8% was effected with 0.5M (NH(4))(2)CO(3) solution. The method was highly sensitive with lower limits of detections to be 10, 20 and 15ngcm(-3) for U(VI), Th(IV) and La(III), respectively, with a better pre-concentration values of 333 for U(VI) and Th(IV) and 400 for La(III), respectively paving way for its applicability in pre-concentrating trace analytes from large sample volumes. The analytical data were within 4.2% R.S.D. reflecting the reproducibility and reliability of the developed method.

Effect of manures on biomass production and pharmacobiochemical properties of some greens.

The present paper deals with the study of biomass production of manures in the greens such as Amaranthus polygamus and Amaranthus viridis of the family Amaranthaceae and Spinacea oleracea of the family Chenopodiaceae. The medicinal uses and pharmaco - phytochemical analysis were also carried out for the plant species which are widely used as greens.

A new chelating sorbent for metal ion extraction under high saline conditions.

A new chelating polymeric sorbent was developed by functionalizing Amberlite XAD-16 with 1,3-dimethyl-3-aminopropan-1-ol via a simple condensation mechanism. The newly developed chelating matrix offered a high resin capacity and faster sorption kinetics for the metal ions such as Mn(II), Pb(II), Ni(II), Co(II), Cu(II), Cd(II) and Zn(II). Various physio-chemical parameters like pH-effect, kinetics, eluant volume and flow rate, sample breakthrough volume, matrix interference effect on the metal ion sorption have been studied. The optimum pH range for the sorption of the above mentioned metal ions were 6.0-7.5, 6.0-7.0, 8.0-8.5, 7.0-7.5, 6.5-7.5, 7.5-8.5 and 6.5-7.0, respectively. The resin capacities for Mn(II), Pb(II), Ni(II), Co(II), Cu(II), Cd(II) and Zn(II) were found to be 0.62, 0.23, 0.55, 0.27, 0.46, 0.21 and 0.25 mmol g(-1) of the resin, respectively. The lower limit of detection was 10 ng ml(-1) for Cd(II), 40 ng ml(-1) for Mn(II) and Zn(II), 32 ng ml(-1) for Ni(II), 25 ng ml(-1) for Cu(II) and Co(II) and 20 ng ml(-1) for Pb(II). A high preconcentration value of 300 in the case of Mn(II), Co(II), Ni(II), Cu(II),Cd(II) and a value of 500 and 250 for Pb(II) and Zn(II), respectively, were achieved. A recovery of >98% was obtained for all the metal ions with 4 M HCl as eluting agent except in the case of Cu(II) where in 6 M HCl was necessary. The chelating polymer showed low sorption behavior to alkali and alkaline earth metals and also to various inorganic anionic species present in saline matrix. The method was applied for metal ion determination from water samples like seawater, well water and tap water and also from green leafy vegetable, from certified multivitamin tablets and steel samples.

A column system for the selective extraction of U(VI) and Th(IV) using a new chelating sorbent.

A new method has been developed using (bis-3,4-dihydroxy benzyl)p-phenylene diamine functionalized to XAD-16 (a polystyrene divinyl benzene copolymer) matrix, to preconcentrate mainly U(VI) and Th(IV) from synthetic and real samples. The developed method is free from matrix interference due to alkali and alkaline metal ions and preconcentrates the actinides with a high degree of selectivity, with consistent trace recoveries. The new chelating resin provides dramatic improvement in metal exchange rate, with half value saturation time (t(1/2)) of less than 1.6 min. The developed method was superior in its metal loading capacity for U(VI) and Th(IV), with values of 0.666 and 0.664 mmol g(-1), respectively. Various physio-chemical properties like effect of solution pH, kinetic studies, resin loading capacity, sample breakthrough volume, matrix effects etc., on metal ion sorption to sorbent phase, were studied using both batch and column method. The new chelatogen was applied to extract U(VI) from near neutral real water samples. Preconcentration and separation of metal ions were possible through pH variation and also by varying the eluant concentration. A high preconcentration factor value of 350 with a lower limit of detection of 20 and 30 ng cm(-3) was obtained for U(VI) and Th(IV), respectively. The practical applicability of the developed resin was examined using synthetic and real samples such as sea/well water samples. The method provides low relative standard deviation values of <3.5% for all analytical measurements, reflecting on the reproducibility and accuracy of the developed method. The new resin is quite durable with recycling time >35 cycles, without any major change in its quantitative metal uptake nature.

Enhanced metal extractive behavior using dual mechanism bifunctional polymer: an effective metal chelatogen.

A new class of chelating polymers using Amberlite XAD-16 (AXAD-16) modified with (N-(3,4-dihydroxy)benzyl)-4-amino,3-hydroxynapthalene-1-sulphonic acid has been developed based on dual mechanism bifunctional polymers, for the extraction of transition and post-transition metal ions. The optimum pH conditions for the quantitative sorption of metal ions were studied. The developed method showed superior extraction qualities with high metal loading capacities of 71, 85, 182, 130 and 46 mg g(-1) for Ni(II), Cd(II), Pb(II), Cu(II) and Co(II), respectively. The rate of metal ion uptake i.e. kinetics studies performed under optimum levels showed a time duration of <5 min except for Co(II) which required 20 min, for complete metal ion saturation. Desorption of metal ions were effective with 15 ml of 2 M HCl/HNO(3) prior to detection using flame atomic absorption spectrophotometer. The chelating polymer was highly ion-selective in nature even in the presence of large concentrations of alkali and alkaline earth metal ions, with a high preconcentrating ability for the metal ions of interest. The developed chelating matrix was tested on its utility with synthetic and real samples like river/sea/tap/well water samples and also with multivitamin/mineral tablets, showed R.S.D. values of <2.5% reflecting on the accuracy and reproducibility of data using the newly developed resin matrix.

Radiometric determination of trace amounts of zinc using liquid scintillation counting.

A sensitive and selective radiometric method of substoichiometric isotope dilution analysis for the determination of trace amounts of zinc is described. The activity of (65)Zn used as a tracer in this method was measured by liquid scintillation counting and its counting efficiency was found to be 76+/-2.7%. The method is based on the extraction of the ion-association complex of zinc from thiocyanate medium at pH 7.9 using substoichiometric amount of Aliquat-336 in toluene. The method is sensitive to 20 ng of Zn(II) in an aqueous phase volume of up to 15 ml and its reliability was tested by applying it to a certified reference material-magnesium alloy and pharmaceutical samples.

Determination of isoniazid in pharmaceutical preparations by reaction with radiochloramine-B.

A method has been developed for the determination of isoniazid (INH) at microgram level in pharmaceutical preparations based on the oxidation of isoniazid by radiochloramine-B. Interference of vitamin C has been overcome by precipitation as lead ascorbate and that of rifampicin and p-aminosalicylic acid by selective extraction. Amounts as low as 25 micrograms of INH can be determined.

Determination of the protonation constant of chloramine-B.

The protonation constant of chloramine-B has been determined at pH < 3.3 by an ionexchange method. The value found is 61 +/- 5.