Determination of the critical period of weed control in corn using a thermal basis

Field studies were conducted over 3 years in southeast Buenos Aires, Argentina, to determine the critical period of weed control in maize (Zea mays L.). The treatments consisted of two different periods of weed interference, a critical weed-free period, and a critical time of weed removal. The Gompertz and logistic equations were fitted to relative yields representing the critical weed-free and the critical time of weed removal, respectively. Accumulated thermal units were used to describe each period of weed-free or weed removal. The critical weed-free period and the critical time of weed removal ranged from 222 to 416 and 128 to 261 accumulated thermal units respectively, to prevent yield losses of 2.5%. Weed biomass proved to be inverse to the crop yield for all the years studied. When weeds competed with the crop from emergence, a large increase in weed biomass was achieved 10 days after crop emergence. However, few weed seedlings emerged and prospered after the 5-6 leaf maize stage (10-20 days after emergence).

Common variants in UMOD associate with urinary uromodulin levels: a meta-analysis.

Uromodulin is expressed exclusively in the thick ascending limb and is the most abundant protein excreted in normal urine. Variants in UMOD, which encodes uromodulin, are associated with renal function, and urinary uromodulin levels may be a biomarker for kidney disease. However, the genetic factors regulating uromodulin excretion are unknown. We conducted a meta-analysis of urinary uromodulin levels to identify associated common genetic variants in the general population. We included 10,884 individuals of European descent from three genetic isolates and three urban cohorts. Each study measured uromodulin indexed to creatinine and conducted linear regression analysis of approximately 2.5 million single nucleotide polymorphisms using an additive model. We also tested whether variants in genes expressed in the thick ascending limb associate with uromodulin levels. rs12917707, located near UMOD and previously associated with renal function and CKD, had the strongest association with urinary uromodulin levels (P<0.001). In all cohorts, carriers of a G allele of this variant had higher uromodulin levels than noncarriers did (geometric means 10.24, 14.05, and 17.67 μg/g creatinine for zero, one, or two copies of the G allele). rs12446492 in the adjacent gene PDILT (protein disulfide isomerase-like, testis expressed) also reached genome-wide significance (P<0.001). Regarding genes expressed in the thick ascending limb, variants in KCNJ1, SORL1, and CAB39 associated with urinary uromodulin levels. These data indicate that common variants in the UMOD promoter region may influence urinary uromodulin levels. They also provide insights into uromodulin biology and the association of UMOD variants with renal function.

Determination of the enantiomers of mianserin, desmethylmianserin, and 8-hydroxymianserin in the plasma and urine of mianserin-treated patients.

An HPLC method is presented which allows the measurement in the same run of the enantiomers of mianserin, desmethylmianserin, and 8-hydroxymianserin in plasma and urine of mianserin-treated patients. Limits of quantitation for the (S)- and (R)-enantiomers of mianserin and desmethylmianserin were 4 and 2.5 ng/ml, respectively, in plasma, and for the (S)- and (R)-enantiomers of mianserin, desmethylmianserin, and 8-hydroxymianserin 5, 2.5, and 5 ng/ml, respectively, in urine. The measured ratios of (S)-mianserin/(R)-mianserin and (S)-desmethylmianserin/(R)-desmethylmianserin in the plasmas of 10 mianserin-treated patients, all extensive metabolizers of debrisoquine as determined by CYP2D6 genotyping, varied, respectively, from 1.0 to 4.06 and from 0.19 to 0.64. As the enantiomers of mianserin differ in their pharmacological profile, these results could partially explain why, until now, no consistent relationship has been established between the therapeutic response and total [(S) + (R)] plasma levels of this antidepressant.

Spectrophotometric determination of cefaclor in pharmaceutical preparations

A simple spectrophotometric method is proposed for the determination of cefaclor. The method involves alkaline hydrolysis of the drug in ammonia buffer solution at pH 10 to yield diketopiperazine-2,5-dione derivative and subsequent measurement at 340 nm. Beer's law is obeyed in the concentration range 1.8 - 55 mg/mL. The proposed method was successfully applied to the determination of cefaclor in pharmaceutical formulations.

Validated spectrofluorometric method for determination of gemfibrozil in self nanoemulsifying drug delivery systems (SNEDDS)

A spectrofluorometric method has been developed and validated for the determination of gemfibrozil. The method is based on the excitation and emission capacities of gemfibrozil with excitation and emission wavelengths of 276 and 304 nm respectively. This method allows de determination of the drug in a self-nanoemulsifying drug delivery system (SNEDDS) for improve its intestinal absorption. Results obtained showed linear relationships with good correlation coefficients (r(2)>0.999) and low limits of detection and quantification (LOD of 0.075 μg mL(-1) and LOQ of 0.226 μg mL(-1)) in the range of 0.2-5 μg mL(-1), equally this method showed a good robustness and stability. Thus the amounts of gemfibrozil released from SNEDDS contained in gastro resistant hard gelatine capsules were analysed, and release studies could be performed satisfactorily.

Development and validation of a high performance liquid chromatographic method for determination of cyclosporine-A from biodegradable intraocular implants

An HPLC method was developed and validated aiming to quantify the cyclosporine-A incorporated into intraocular implants, released from them; and in direct contact with the degradation products of PLGA. The separation was carried out in isocratic mode using acetonitrile/water (70:30) as mobile phase, a C18 column at 80 ºC and UV detection at 210 nm. The method provided selectivity based on resolution among peaks. It was linear over the range of 2.5-40.0 µg/mL. The quantitation and detection limits were 0.8 and 1.2 µg/mL, respectively. The recovery was 101.8% and intra-day and inter-day precision was close to 2%.

Development of an optical redox chemical sensor for nitrite determination

An optical chemical sensor for the determination of nitrite based on incorporating methyltrioctylammonium chloride as an anionic exchanger on the triacetylcellulose polymer has been reported. The response of the sensor is based on the redox reaction between nitrite in aqueous solution and iodide adsorbed on sensing membrane using anion exchange phenomena. The sensing membrane reversibly responses to nitrite ion over the range of 6.52×10-6 - 8.70×10-5 mol L-1 with a detection limit of 6.05×10-7 mol L-1 (0.03 µg mL-1) and response time of 6 min. The relative standard deviation for eight replicate measurements of 8.70×10-6 and 4.34×10-5 mol L-1 of nitrite was 4.4 and 2.5 %, respectively. The sensor was successfully applied for determination of nitrite in food, saliva and water samples.

Simultaneous determination of four phenolic compounds in extracts of aerial parts of Ipomoea pes-caprae (L.) R. Br. (Convolvulaceae) by HPLC-UV

Among other applications, Ipomoea pes-caprae is popularly used to treat jellyfish stings, supporting the development of a product for dermatological use. Hydroethanolic spray-dried extract was chosen for the further development of phytomedicines, and a stability-indicative HPLC-UV method was developed and validated for the determination of isoquercitrin and isochlorogenic acids A, B and C. The method was developed using a C18 column (250 x 4.6 mm, 5 µm) with an acetonitrile:water mobile phase at pH 3.0 in a gradient run. The four constituents and other unidentified components of the extract were appropriately resolved without interference of degradation products after stress tests (acid, alkali, neutral, oxidant, photolysis). The method showed linearity in the isoquercitrin concentration range from 5.0-50.0 µg mL-1, with adequate precision (RSD% < 2.5% for the intra- and inter-day studies), accuracy (recovery of 100.0 ± 2.0%), and robustness. Both the herbal drug and spray-dried extract of I. pes-caprae were subjected to stability studies in accelerated and long-term conditions over four months. The samples maintained their characteristics and marker contents (< 10% of variation).

Use of experimental design in the optimisation of a solid phase preconcentration system for Cobalt determination by GFAAS

In this work is proposed a solid phase preconcentration system of Co2+ ions and its posterior determination by GFAAS in which fractional factorial design and response surface methodology (RSM) were used for optimization of the variables associated with preconcentration system performance. The method is based on cobalt extraction as a complex Co2+-PAN (1:2) in a mini-column of polyurethane foam (PUF) impregnated with 1-(2-pyridylazo)-naphthol (PAN) followed by elution with HCl solution and its determination by GFAAS. The chemical and flow variables studied were pH, buffer concentration, eluent concentration and preconcentration and elution flow rates. Results obtained from fractional factorial design 2(5-1) showed that only the variables pH, buffer concentration and interaction (pH X buffer concentration) based on analysis of variance (ANOVA) were statistically significant at 95% confidence level. Under optimised conditions, the method provided an enrichment factor of 11.6 fold with limit of detection and quantification of 38 and 130 ng L-1, respectively, and linear range varying from 0.13 to 10 µg L-1. The precision (n = 9) assessed by relative standard deviation (RSD) was respectively 5.18 and 2.87% for 0.3 and 3.0 µg L-1 cobalt concentrations.

Sensitive spectrophotometric determination of lansoprazole in pharmaceuticals using ceric ammonium sulphate based on redox and complex formation reactions

Two simple sensitive and cost-effective spectrophotometric methods are described for the determination of lansoprazole (LPZ) in bulk drug and in capsules using ceric ammonium sulphate (CAS), iron (II), orthophenanthroline and thiocyanate as reagents. In both methods, an acidic solution of lansoprazole is treated with a measured excess of CAS followed by the determination of unreacted oxidant by two procedures involving different reaction schemes. The first method involves the reduction of residual oxidant by a known amount of iron(II), and the unreacted iron(II) is complexed with orthophenanthroline at a raised pH, and the absorbance of the resulting complex measured at 510 nm (method A). In the second method, the unreacted CAS is reduced by excess of iron (II), and the resulting iron (III) is complexed with thiocyanate in the acid medium and the absorbance of the complex measured at 470 nm (method B). In both methods, the amount CAS reacted corresponds to the amount of LPZ. In method A, the absorbance is found to increase linearly with the concentration of LPZ where as in method B a linear decrease in absorbance occurs. The systems obey Beer's law for 2.5-30 and 2.5-25 µg mL-1 for method A and method B, respectively, and the corresponding molar absorptivity values are 8.1×10³ and 1.5×10(4) L mol-1cm-1 . The methods were successfully applied to the determination of LPZ in capsules and the results tallied well with the label claim. No interference was observed from the concomitant substances normally added to capsules.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 silica in the determination of copper

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol for determination of Cu(II) ions in sugar cane spirit (cachaça) is described, based on differential pulse anodic stripping voltammetry (DPASV) procedure. The Cu(II) oxidation peak was observed at 0.03 V (vs. SCE) in phosphate solution (pH 3.0). The results were obtained using optimised conditions such as 100 mV pulse amplitude, 3 min accumulation time, 25 mV s-1 scan rate in phosphate solution pH 3.0, resulting in a linear dynamic range from 8.0 x 10-7 to 1.0 x 10-5 mol L-1 Cu(II) and a limit of detection 2.0 x10-7 mol L-1. Cu(II) spiked in a cachaça sample was determined with 102.5 % mean recovery at mmol L-1 level. Interference from other metallic cations present in the sample was avoided by the standard addition procedure.

Direct determination of calcium in milk by atomic absorption spectrometry using flow-injection analysis

A flow-injection system with sample and reagent addition by the synchronous merging zones approach for calcium determination in milk by flame AAS is proposed. Main parameters were optimized using a factorial design with central point. The optimum conditions were 2.5% (m/v) for La concentration, 8 mL min-1 for the carrier flow-rate, 20 cm for coiled reactor and 250 ìL for sample volume. Different sample preparation procedures were evaluated such as dilution in water or acid and microwave-assisted decomposition using concentrated or diluted acids. The optimized flow system was applied to determine Ca in eleven commercial milk samples and two standard reference materials diluted in water. Similar calcium levels were encountered comparing the results obtained by the proposed method (dilution in water) with those obtained using microwave-oven digestion. Results obtained in two standard reference materials were in agreement at 95% confidence level with those certified. Recoveries of spiked samples were in the 93% - 116% range. Relative standard deviation (n = 12) was < 5.4% and the sample throughput was 150 measurements per hour, corresponding to a consumption of 250 µL of sample and 6.25 mg La per determination.

A simple method for the spectrophotometric determination of cephalosporins in pharmaceuticals using variamine blue

A simple spectrophotometric method for the determination of cefotaxime, ceftriaxone, cefadroxil and cephalexin with variamine blue is presented. The determination is based on the hydrolysis of β-lactam ring of cephalosporins with sodium hydroxide which subsequently reacts with iodate to liberate iodine in acidic medium. The liberated iodine oxidizes variamine blue to violet colored species of maximum absorption at 556 nm. The absorbance is measured within the pH range of 4.0-4.2. Beer's law is obeyed in the range of 0.5-5.8 µg mL-1, 0.2-7.0 µg mL-1, 0.2-5.0 µg mL-1 and 0.5-8.5 µg mL-1 for cefotaxime, ceftriaxone, cefadroxil and cephalexin respectively. The analytical parameters were optimized and the method is successfully applied for the determination of cefotaxime, ceftriaxone, cefadroxil and cephalexin in pharmaceuticals.

Atividade de três drogas antivirais sobre os herpesvírus bovino tipos 1, 2 e 5 em cultivo celular

A atividade de três fármacos antivirais (Aciclovir [ACV], Ganciclovir [GCV] e Foscarnet [PFA]) foi testada in vitro frente aos herpesvírus bovino tipos 1 (BoHV-1), 2 (BoHV-2) e 5 (BoHV-5). Para isso, utilizou-se o teste de reducao de placas virais em cultivo celular, testando-se diferentes concentracoes dos farmacos frente a 100 doses infectantes para 50% dos cultivos celulares (DICC50) dos respectivos virus. Pelo teste de MTT (3-(4,5-Dimethylthiazol- 2-yl)-2,5-diphenyltetrazolium bromide), verificou-se que concentracoes inferiores a 200ƒÊg/mL dos tres antivirais resultaram em indices de viabilidade de celulas MDBK e Hep2 superiores a 80%. Com base na concentracao citotoxica para 50% das celulas (CC50) e na concentracao dos farmacos efetiva para inibir em 50% o numero de placas virais (EC50), calculou-se o indice de seletividade (IS) dos antivirais para os tres herpesvirus. Assim, o ACV demonstrou ser moderadamente ativo frente ao BoHV-1 (EC50: 112,9ƒÊg/mL e IS: 4,5), ao BoHV-2 (EC50: 114,2 ƒÊg/mL e IS: 4,5) e BoHV-5 (EC50: 96,9ƒÊg/mL e IS: 5,3). O GCV apresentou atividade moderada frente ao BoHV-2 (EC50: 33,5ƒÊg/mL e IS: 16,6) e, em menor grau, contra o BoHV-5 (EC50: 123,2ƒÊg/mL e IS: 4,5), sendo ineficaz frente ao BoHV-1 (EC50: 335,8ƒÊg/mL e IS: 1,7). O PFA apresentou atividade antiviral mais pronunciada, sendo o unico farmaco que, na concentracao de 100ƒÊg/mL, inibiu completamente a producao de placas pelos tres virus testados. O PFA foi o mais efetivo in vitro frente ao BoHV-1 (EC50: 29,5ƒÊg/mL e IS: 42,2), ao BoHV-2 (EC50: 45,2ƒÊg/mL e IS: 27,6) e ao BoHV-5 (EC50: 7,8ƒÊg/mL e IS: 160,6). Portanto, os resultados obtidos indicam que o PFA pode se constituir em um candidato para terapia experimental de infeccoes pelos herpesvirus de bovinos in vivo.

Extraction and Simultaneous Determination of Glyphosate, AMPA and Compounds of the Shikimic Acid Pathway in Plants

This study has aimed to develop a method for simultaneous extraction and determination by liquid chromatography and mass spectrometry (LC-MS/MS) of glyphosate, aminomethylphosphonic acid (AMPA), shikimic acid, quinic acid, phenylalanine, tyrosine and tryptophan. For the joint analysis of these compounds the best conditions of ionization in mass spectrometry and for chromatographic separation of the compounds were selected. Calibration curves and linearity ranges were also determined for each compound. Different extraction systems of the compounds were tested from plant tissues collected from sugarcane (Saccharum officinarum) and eucalyptus (Eucalyptus urophylla platiphylla) plants two days after the glyphosate application at the dose of 720 g a.e. ha-1. The plant material was dried in a forced air circulation drying oven and in a lyophilizer, and subsequently the extractions with acidified water (pH 2.5), acetonitrile-water (50:50) [v/v] and methanol-water (50:50) [v/v] were tested. To verify the recovery of the compounds in the plant matrix with acidified water as an extracting solution, the samples were fortified with a solution containing the mixture of the different analytical standards present so that this one presented the same levels of 50 and 100 μg L-1 of each compound. All experiments were conducted with three replicates. The analytical method developed was efficient for compounds quantifications. The extraction from the samples dried in an oven and using acidified water allowed better extraction levels for all compounds. The recovery levels of the compounds in the fortified samples with known amounts of each compound for both plants samples were rather satisfactory.