Preliminary study of HCHO spatial and temporal distribution from Coastal to Plateau areas in Antarctica

Formaldehyde concentrations were determined in over 1800 snow samples (snowpit, firn cores and superficial snow) from Antarctica by a sensitive spectrofluorimetric Flow Injection Analysis method. The method performances (detection limit: 55?ng/L; reproducibility: 2.5% at 1?µg/L level; linear range: 0.1–3000?µg/L) allowed a reliable determination of formaldehyde content in all the collected samples. The range of determined concentrations was 0–70?µg/L with a mean concentration of 7.7?µg/L and a median concentration of 5.8?µg/L. The formaldehyde background level was estimated at a few micrograms per liter in coastal and plateau areas of Northern Victoria Land. In some stations the background values are modulated by HCHO deposition events recurring over relatively large time periods.     

Selenium speciation in soil extracts using LC-ICP-MS

Selenium (Se) speciation in soil affects its bioavailability to crops. An analytical procedure for the determination of inorganic Se species (selenite and selenate) in soil extracts by anion-exchange liquid chromatography (LC) with ICP-MS detection has been developed, with 10-fold higher sensitivity than existing HGAAS-based soil Se measurements. A comparison of phosphate extraction solutions on agricultural soils amended with 20?µg?kg^–1 selenate or selenite was carried out, and a 0.016?M?KH₂PO₄ extraction solution is recommended. Recovery of selenate was >91%; however, selenite recovery ranged between 18.5% and 46.1%, due to rapid binding to the soil. Soil preparation did not have a significant (p?>?0.05) effect on the extractability of the selenate or selenite amendments. The stability of Se species in the phosphate extracts was variable, depending on temperature and storage time. Therefore, immediate (<1?h) analysis of the soil extracts is preferable. The method developed was applied to the determination of extractable Se from six arable soils in the UK. Extractable Se levels in these soils ranged between 6 and 13?µg?kg^–1 consisting of selenite and some soluble organic Se.     

Comparative study of potentiometric and amperometric tissue-based electrodes for oxalate

Acetone-precipitated pulp from banana skins is physicall entrapped at the tip of a carbon dioxide gas-sensor and on a hydrogen peroxide sensor probe to determine oxalate potentiometrically and amperometrically in aqueous solution and inurine. The enzyme present in the tissue is oxalate oxidase. The potentiometric response has a slope of 47–50 mV/decade for 1 × 10^?4 M–2 × 10^?3 M oxalate with a detection limit of 2 × 10^?5 M. The amperometric response is linear for 2 × 10^t-5–3 × 10^?4 M oxalate with a dectection limit of 2 × 10^?6 M. Average recoveries of oxalate added to aqueous samples were 96.2% and 98.0%, and average relative standrd deviations were 3.8% and 3.6% for the potentiometric and amperometric systems, respectively. Oxalate was determined in six control urine samples, with relative errors of about 2.5%, by both electrode systems after a simple clean-up.     

A Highly Sensitive and Selective Enzymatic Biosensor Based on Direct Electrochemistry of Hemoglobin at Zinc Oxide Nanoparticles Modified Activated Screen Printed Carbon Electrode

A sensitive enzymatic biosensor has been developed for the detection of hydrogen peroxide (H₂O₂), nitrite ( ) and trichloroacetic acid (TCA) by using hemoglobin (Hb) immobilized on activated screen printed carbon electrode (ASPCE) and zinc oxide (ZnO) composite. A pair of well defined redox peaks is observed with a heterogeneous electron transfer rate constant (K_s) of 5.27 s^?1 for Hb at ASPCE/ZnO. The biosensor exhibits the detection of H₂O₂, TCA and in the concentration range of 0.5–129.5 µmol L^?1, 2.5–72.5 mmol L^?1 and 0.2–674 µmol L^?1 with the detection limit of 0.083 µmol L^?1, 0.12 mmol L^?1 and 0.069 µmol L^?1, respectively.     

Thermal, UV, FTIR, and XRD studies of urinary stones

Various crystals are seen in human urine. Oxalate, Phosphate, Uric acid, and Urate crystals are generally seen in urinary calculi. Calcium stones are most common, comprising 75 % of all urinary calculi. They may be pure calcium oxalate or calcium phosphate or a mixture of both. Many stones are not homogeneous. Low calcium intake increases the intestinal absorption of calcium, thus decreasing the amount of calcium available in the intestinal tract to form insoluble complexes with Oxalate. Consequently, a higher amount of oxalate is available for intestinal absorption and as a result, urinary oxalate excretion increases. Mineral water consumption did not reduce urinary oxalate excretion. High urinary excretion and concentration of magnesium decrease both the nucleation and growth rates of calcium oxalate crystals in urine, because of the higher solubility of magnesium oxalate compared with calcium oxalate. Analytical results show calcium oxalate to be one of the major inorganic components of renal stones and found to be present in almost all kidney and bladder stones. About 39.5 % of the total composition of the calculi is found to contain purely calcium oxalate and also hydroxyl apatite. The ten samples are a mixture of calcium oxalate and phosphate stones. Four samples are calcium oxalate as major composition and the remaining are calcium phosphate as major composition. These kidney stones are taken photographically and size of the stone are measured using optical microscopy. These qualitative analyses are also confirmed by UV, FTIR, DSC, and XRD analysis.     

Micellar liquid chromatographic method for the determination of ephedrine and pseudoephedrine in human serum by direct inject of the sample with simple dilution

A micellar high-performance liquid chromatographic method was developed to simultaneously determine ephedrine and pseudoephedrine in human serum. The serum sample pretreatment was a simple dilution in a micellar solution, filtration, and direct injection, thus avoiding time-consuming and tedious steps. Hence, there is no need to use an internal standard. The serum samples were analyzed using a mobile phase containing 1.50?×?10^?1?mol/L sodium dodecyl sulfate and 0.02?mol/L sodium dihydrogen phosphate with 7.5% (v/v) 1-propanol at pH 3.0, running at 1.0?mL/min by an Inertsil C18 (150?×?4.6?mm, 5?µm) column at 30°C. The UV wavelength was set at 210?nm. The developed method was validated by linearity (r?>?0.9990) and intra- and inter-day precisions of ephedrine and pseudoephedrine (relative standard deviation; RSD%, 0.04–10.40, and RSD %, 0.30–10.25, respectively), LODs for ephedrine and for pseudoephedrine was 2.63 and 2.70?µg/mL, respectively; lower limit of quantification for ephedrine and for pseudoephedrine was 4.38 and 4.51?µg/mL, respectively. Finally, the proposed method was applied to investigate ephedrine and pseudoephedrine in real human serum samples after oral administration of Kechuanning Koufye including Ephedra herb. It is environmentally friendly, easy-to-handle, and feasible method for routine analysis in clinical laboratory.     

Assessment of Heavy Metal Pollution and Ecological Risk of Roadside Soils in Tlemcen (Algeria) Using Flame-Atomic Absorption Spectrometry

In Algeria, few studies have been conducted on the evaluation of roadside soil pollution. A total of 34 soil samples (28 roadside and 6 off-road) was obtained at 0–20?cm depth along the RN 35 national road. Heavy metal (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) contents were extracted using aqua regia digestion and determined using atomic absorption spectrometry. Background values of heavy metal contents were determined using the robust statistical method of median plus two times the median absolute deviation. Single- and multi-element pollution and ecological risk indices were calculated. The results showed that background values were 2.5?±?0.3, 64.9?±?8.1, 28.0?±?4.1, 29371.5?±?4403.0, 32.9?±?4.4, 72.2?±?12.8, and 445.1?±?62.9?mg/kg for Cd, Cr, Cu, Fe, Ni, Pb, and Zn, respectively. The results were all higher than their corresponding median values. Single-element pollution indices (enrichment factor and geoaccumulation index) showed that the pollution is primarily due to Pb and Zn. Multi-element pollution index (Nemerow index) indicated that only 3% of the soil samples are strongly contaminated, whereas 23% are seriously contaminated. The potential ecological risk index showed that Cd is the most harmful element, followed by Pb and Zn. 65% of the soil samples had moderate potential ecological risk, while only 3% had considerable potential ecological risk. This study may be used as a baseline for future monitoring and as a tool for decision-making regarding environmental protection policies and sustainability of this semiarid agroecosystem.     

In vitro and in silico study of Aloe vera leaf extract against human breast cancer

Abstract

Aloe vera leaf contains some bioactive compounds that have a strong binding affinity toward estrogen receptor as compared to standard drug tamoxifen. In this study, we have found that the IC₅₀ of Aloe vera leaf extract against breast cancer cell line (MCF-7) is 23?µg/mL which is much lower than the IC₅₀ (332?µg/mL) of Aloe vera leaf extract against non-cancerous cell line (NIH-3T3). We have also calculated the total concentration of phenolic acid (385.662?µg/mL), flavonoids (160.402?µg/mL) and alkaloids (276.754?µg/mL) in Aloe vera leaf extract. The free radical scavenging activity of Aloe vera leaf extract is 67% to 89% (at 50 to 300?µg/ml). Our virtual molecular docking study suggests that bioactive compounds like Aloe-emodin (?8.8?Kcal/mol), 7-hydroxy-2,5 dimethylchromone (?7.5?Kcal/mol), Beta-sitosterol (?7.3?Kcal/mol) etc. have a greater binding affinity toward estrogen alpha receptor as compared to standard drug Tamoxifen (?6.4?Kcal/mol).

     

Development and validation of a RP-HPLC method for simultaneous quantification of bedaquiline (TMC207), moxifloxacin and pyrazinamide in a pharmaceutical powder formulation for inhalation

A reversed phase high performance liquid chromatography (RP-HPLC) method for the simultaneous quantification of bedaquiline (TMC207), moxifloxacin and pyrazinamide in a pharmaceutical powder formulation for inhalation has been developed and validated. The powder was simply dissolved in methanol and the analytes separated in a run time of 20?min on a Luna C18 (2) (150?×?4.6?mm, 5?µm) column using gradient elution with methanol and triethylamine phosphate buffer (pH 2.5) delivered at 1.2?mL/min. The detection (with retention time) was carried out at 269?nm (2.9?min) for pyrazinamide, 296?nm (7.0?min) for moxifloxacin and 225?nm (16.3?min) for bedaquiline, respectively. The method was linear for all analytes in the concentration range 1-100?µg/mL with correlation coefficients >0.998. Lower limits of quantitation (µg/mL) of bedaquiline, moxifloxacin and pyrazinamide were 0.56, 0.43 and 0.24, respectively. The method was accurate (relative error in the range ?0.2 to 2.2) and precise (%RSD ≤6.2) with recovery in the range 100.0–104.7%. The method was successfully applied to determine the drug content and content uniformity of the three analytes in a spray-dried combination powder formulation for inhalation containing L-leucine.     

Application of Pyrolysis Cryogenic Trap Gas Chromatography/Atomic Emission Detection (Py-CryT-GC/AED) for the Study of Nitrogen Forms and Dynamics in a Grassland Soil

Soil organic nitrogen (N) was characterized for its chemical species and chemical transformations in a grassland soil profile by using a combination of cryogenic pyrolysis gas chromatography atomic emission detection method with soil physical size fractionation. The soils taken from 0–12, 12–25, and 25–38 cm depth layers were separated into five fractions, <2, 2–38, 38–53, 53–105, and 105–250 µm and each of which was analyzed for total organic C and N, and different N forms. Our results showed that (1) total organic carbon has a positive correlation with the total organic nitrogen (TON) with correlation coefficient increased with soil depth; (2) deep and small particle-size fraction soils yielded more volatile pyrolysate N than the surface and large particle-size fractions and the amount of volatile pyrolysate N has a linear positive correlation with TON and correlation coefficient increased with soil depth; (3) the major components of the volatile pyrolysate N include ammonia, acetonitrile, hydrogen cyanide, pyridine, and pyrrole; (4) of the total volatile pyrolysate N, ammonia accounted for more than 40%, and the sum of acetonitrile and hydrogen cyanide accounted for approximately 30–50%; and (5) the amounts of acetonitrile, hydrogen cyanide, and pyridine had increased positive correlations with TON with increasing soil depth, but the correlation between the amount of pyrrole and depth decreased in the opposite direction. Our research result sheds some light into soil organic nitrogen forms and its transformations in the processes of soil organic C aging and stabilization.     

Distribution of arsenic species in the freshwater crustacean Procambarus clarkii

The concentrations of total arsenic and arsenic species in the complete organism of the crayfish Procambarus clarkii and its various parts (hepatopancreas, tail, and remaining parts) were analyzed in order to discover the distribution of arsenic and its species. With this information it will be possible to establish where the chemical forms of this metalloid tend to accumulate and what risks may derive from the contents and species present in the edible parts of this crustacean. The total arsenic content in the complete organism and in the various parts analyzed ranged from 2.5 to 12 µg g^?1 dry mass (DM), with inorganic arsenic representing 18 to 34% of total arsenic. The arsenical composition varied according to the part of the crayfish considered. The hepatopancreas had the highest levels of total arsenic (9.2–12 µg g^?1 DM) and inorganic arsenic (2.7–3.2 µg g^?1 DM). The tail (edible part) had the lowest levels of both total arsenic (2.5–2.6 µg g^?1 DM) and inorganic arsenic (0.46–0.64 µg g^?1 DM). The predominant organoarsenical species were the dimethylarsinoylribosides: glycerol riboside in the hepatopancreas, sulfate riboside in the tail, and sulfonate and phosphate ribosides in the remaining parts. Copyright © 2002 John Wiley & Sons, Ltd.     

Chemical modification of poly(substituted-acetylene). I. Synthesis and gas permeability of poly(1-trimethylsilyl-1-propyne)/poly (dimethylsiloxane) graft copolymer

In order to improve the selectivity and the stability and the stability for gas permeation of poly (1-trimethylsilyl-1-propyne) (PTMSP) membrane, it was chemically modified by grafting polydimethylsiloxane (PDMS) chains. The graft copolymers were synthesized by four different methods via metallation of PTMSP with n-butyllithium. PDMS content of the graft co-polymers was controlled in the range of 4–92 mol %. Very tough, thin membranes could be prepared from these graft copolymers using a solvent casting method. Thermal property and gas permeability of the copolymer membranes thus obtained were evaluated. These membranes were relatively thermally stable, and the softening points were over about 150°C. Oxygen permeability coefficients Po₂ and selectivity Po₂/PN₂ of PTMSP/PDMS graft copolymers depended on the PDMS content, the former was in the range of 1 X 10^?8 to 2 × 10^?7 cm³ (STP)· cm/(cm²· s · cm. Hg) and the latter was 2.0–3.1. Minimum values of PO₂ and PN₂ occured at PDMS content of about 55 mol %. The introduction of more than 60 mol % of PDMS resulted in oxygen permeability coefficient which was maintained for more than one moth (PO₂ = 2 ? 6 × 10 ^?8 cm ³ (STP)· cm/(cm²·s·cm Hg), PO₂/PN₂ = 2.3–2.7).     

Electrocatalytic Oxidation and Determination of Hydrazine at an AuCu Nanoparticles – Graphene – Ionic Liquid Composite Film Coated Glassy Carbon Electrode

Gold‐copper alloy nanoparticles (AuCu NPs) were electrodeposited on a graphene – ionic liquid composite film (EGN‐IL). The AuCu NPs showed high electrocatalysis to the oxidation of hydrazine with a catalytic reaction rate constant of about 5.0×10⁴ mol/Ls. In phosphate buffer solutions (pH 6.8) the oxidation current of hydrazine at 0.15 V (vs. SCE) at the resulting electrode (AuCu? EGN‐IL/GCE) was linear to its concentration in the range of 0.2–110 µM with a sensitivity of 56.7 µA/mM, and the detection limit was 0.1 µM (S/N=3). The electrode was successfully applied to the determination of waste water.     

Thermal decomposition of cerium oxalate and mixed cerium-gadolinium oxalates

Cerium oxalate and mixed cerium-gadolinium oxalates containing 20 and 50 mol% gadolinium were subjected to thermal decomposition. Thermal analysis showed that cerous oxalate is transformed to cerium oxide in two steps. The first step involves the endothermic removal of 10 mol of water, with a calculated activation energy of 78.2 kJ/mol. The second step involves the exothermic decomposition of the anhydrous oxalate, with an activation energy of 112.6 kJ/mol. The water content in the mixed cerium-gadolinium oxalates decreases with increasing gadolinium content, while the temperature of exothermic decomposition of the anhydrous oxalate increases with it.

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Zusammenfassung Zeroxalat und Zer-Gadolinium-Mischoxalat mit 20 bzw. 50 mol% Gadolinium wurden einer thermischen Zersetzung unterzogen. Die Thermoanalyse zeigte, da\ Zeroxalat in zwei Schritten in Zeroxid überführt wird. Der erste Schritt mit der Aktivierungsenergie von 78.2 kJ/mol besteht in der endothermen Abgabe von 10 mol Wasser. Der zweite Schritt mit der Aktivierungsenergie 112.6 kJ/mol umfa\t die exotherme Zersetzung des wasserfreien Oxalates. Der Wassergehalt der Zer-Gadolinium-Mischoxalate nimmt mit steigendem Gadoliniumgehalt ab und die Temperatur für den exothermen Zersetzungsvorgang der wasserfreien Oxalate nimmt mit steigendem Gadoliniumgehalt zu.

     

Synthesis,characterization, antitumor,and cytotoxic activity of mononuclear Ru(II) complexes

In the search for antitumor active metal complexes several ruthenium complexes have been reported to be promising. A series of mononuclear Ru(II) complexes, [Ru(T)₂(S)]²⁺, where T?=?2,2′-bipyridine/1,10-phenanthroline and S?=?CH₃-bitsz, Cl-bitsz, Br-bitsz, tmtsz, dmtsz, have been prepared and characterized by UV-Vis, IR, ¹H-NMR, FAB-mass spectroscopy, and elemental analysis. The complexes were subjected to in vivo anticancer activity against a transplantable murine tumor cell line Ehrlich's ascitic carcinoma (EAC) and in vitro cytotoxic activity against human cancer cell line Molt 4/C₈, CEM, and murine tumor cell line L1210. Ruthenium complexes showed promising biological activity especially in decreasing tumor volume and viable ascitic cell counts. Treatment with these complexes prolonged the life span of EAC-tumor-bearing mice by 10–48%. In vitro evaluation of these ruthenium complexes revealed cytotoxic activity from 0.21 to 24?µmol?L^?1 against Molt 4/C₈, 0.16–19?µmol?L^?1 against CEM, and 0.75–32?µmol?L^?1 against L1210 cell proliferation, depending on the nature of the compound.     

Synthesis of Functionalized MWCNTs Decorated with Copper Nanoparticles and Its Application as a Sensitive Sensor for Amperometric Detection of H2O2

Functionalized‐multiwall carbon nanotubes decorated with redox active copper nanoparticles have been fabricated for sensitive enzyme‐less H₂O₂ detection. The new nanocomposite was characterized by Transmission electron microscopy, energy dispersive X‐ray analysis and cyclic voltammetry. The response of the modified electrode to H₂O₂ was examined using amperometry at ?0.45 V vs. Ag/AgCl in a buffer solution at pH 10.0. The developed sensor displayed linear concentration ranges of 0.5–10.0 and 10.0–10000.0 µmol L^?1 with a detection limit of 0.3 µmol L^?1. The proposed sensor displayed good selectivity for H₂O₂ detection in the presence of common interferences such as ascorbic acid.     

Analysis of long-chain fatty acids in grey wastewater with in-vial derivatisation

The presence and levels of long-chain fatty acids (C₆–C₂₀) in grey wastewater from bathrooms have been investigated. The acids were purified and concentrated by solid-phase extraction on strong anion exchange discs, in-vial derivatised to their corresponding methyl ester and subsequently analysed by GC-MS. The method was able to quantify the acids at concentration <1?µg/L with a recovery of 31–97%. The levels of fatty acids were found in the range of <0.5 to 27?100?µg/L and the highest levels were found for the saturated lauric (C₁₂), palmitic (C₁₆) and stearic (C₁₈) acids. The treatment efficiency of a local treatment plant was evaluated by comparing concentrations of fatty acids at the inlet and the outlet. It was found that the treatability decreases with increasing chain length for the saturated acids (19–100% degradation) whereas the corresponding mono unsaturated acids were more easily degraded.     

Daily cycle of variability contents of phosphorus forms in surface microlayer of a light salinity Baltic Sea Lagoon lake (North Poland) — Part II

A daily cycle of tests was conducted to specify the concentration variation of phosphorous compounds and other chemical parameters at surface microlayers of a shallow lagoon lake located on the Baltic Coast. The water for analyses was collected from Lake Do?gie Wielkie in one hour cycles for the period of 24 hours. Samples were collected from the surface microlayers that had a thickness of 80–115 µm and 250–300 µm as well as from the subsurface water at the depth of 15 cm. Data analysis shows information concerning the migration of phosphorous compounds between the analyzed layers. Correlations were estimated for the obtained concentrations of phosphorous compounds and the nitrogen compounds and other physico-chemical values which were described in the first part of the cycle. The content of nutrients in the examined surface water layers correlated with the oxygen consumption due to the value of the oxygen consumption mostly depending on the concentration of organic matter.     

Polychlorinated biphenyls,dibenzo-p-dioxins and dibenzofurans in soil samples from airport areas of Croatia

Levels and patterns of polychlorinated biphenyls (PCBs) were studied in surface soil samples collected in the coastal part of Croatia within and surrounding four different airports and in the vicinity of two partially devastated electrical transformer stations. The compounds accumulated from air-dried soil samples by multiple ultrasonic extraction with an n-hexane?:?acetone 1?:?1 mixture were analysed by capillary gas chromatography with electron capture and ion-trap detection. PCBs were quantified against a standard Aroclor 1242/Aroclor 1260 mixture and a standard mixture of 17 individual PCB congeners (IUPAC No.: 28, 52, 60, 74, 101, 105, 114, 118, 123, 138, 153, 156, 157, 167, 170, 180, and 189). The mass fractions of total PCBs in 18 soil samples collected within the airport premises ranged from 3 to 41?327?µg/kg dry weight (dw) (median: 533?µg/kg?dw), and those in 21 samples collected at a distance ranging from several metres to 5?km away from the airport fence, from <1 to 39?µg/kg?dw (median: 5?µg/kg?dw). The highest PCB levels were determined in soils along the airport aprons where the aircrafts were serviced and refuelled. The PCB pattern was very similar to technical Aroclor 1260 in all airport soils. The PCB pattern in 22 soils collected in the vicinity of electrical transformer stations was dominated by congeners contained in Aroclor 1242. These soils contained 7 to >400?µg/kg?dw of total PCBs. One highly PCB-contaminated airport soil sample was analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). With an international toxic equivalent (I-TEQ) of 9.7?ng/kg?dw, the airport soil contamination was within values typical for urban and rural areas, and the congener patterns gave no clear indication for PCBs as the only source of PCDDs/PCDFs.