A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids

A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form) in non-aqueous media. The anion loading of the AER (OH− form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.

Brazilian maize genotypes sensitivity to water deficit estimated through a simple crop yield model

The objective of this work was to determine the sensitivity of maize (Zea mays) genotypes to water deficit, using a simple agrometeorological crop yield model. Crop actual yield and agronomic data of 26 genotypes were obtained from the Maize National Assays carried out in ten locations, in four Brazilian states, from 1998 to 2006. Weather information for each experimental location and period were obtained from the closest weather station. Water deficit sensitivity index (Ky) was determined using the crop yield depletion model. Genotypes can be divided into two groups according to their resistance to water deficit. Normal resistance genotypes had Ky ranging from 0.4 to 0.5 in vegetative period, 1.4 to 1.5 in flowering, 0.3 to 0.6 in fruiting, and 0.1 to 0.3 in maturing period, whereas the higher resistance genotypes had lower values, respectively 0.2-0.4, 0.7-1.2, 0.2-0.4, and 0.1-0.2. The general Ky for the total growing season was 2.15 for sensitive genotypes and 1.56 for the resistant ones. Model performance was acceptable to evaluate crop actual yield, whose average errors estimated for each genotype ranged from -5.7% to +5.8%, and whose general mean absolute error was 960 kg ha-1 (10%).

Rapid LC-MS/MS quantification of the major benzodiazepines and their metabolites on dried blood spots using a simple and cost-effective sample pretreatment.

BACKGROUND: Dried blood spots (DBS) sampling has gained popularity in the bioanalytical community as an alternative to conventional plasma sampling, as it provides numerous benefits in terms of sample collection and logistics. The aim of this work was to show that these advantages can be coupled with a simple and cost-effective sample pretreatment, with subsequent rapid LC-MS/MS analysis for quantitation of 15 benzodiazepines, six metabolites and three Z-drugs. For this purpose, a simplified offline procedure was developed that consisted of letting a 5-µl DBS infuse directly into 100 µl of MeOH, in a conventional LC vial. RESULTS: The parameters related to the DBS pretreatment, such as extraction time or internal standard addition, were investigated and optimized, demonstrating that passive infusion in a regular LC vial was sufficient to quantitatively extract the analytes of interest. The method was validated according to international criteria in the therapeutic concentration ranges of the selected compounds. CONCLUSION: The presented strategy proved to be efficient for the rapid analysis of the selected drugs. Indeed, the offline sample preparation was reduced to a minimum, using a small amount of organic solvent and consumables, without affecting the accuracy of the method. Thus, this approach enables simple and rapid DBS analysis, even when using a non-DBS-dedicated autosampler, while lowering the costs and environmental impact.

Simple and multiple resistances to viruses in cowpea genotypes

The objective of this work was to identify new sources of simple and multiple resistances to Cowpea severe mosaic virus (CPSMV), Cowpea aphid-borne mosaic virus (CABMV) and Cucumber mosaic virus (CMV) isolates in cowpea (Vigna unguiculata). Thirty-three genotypes from the germplasm bank of Universidade Federal do Ceará were tested as to their resistance to four CPSMV isolates, two CABMV isolates and one CMV isolate. Twenty-five days after the first virus inoculations, all inoculated plants, including the asymptomatic ones, were tested by serology. Genotypes were classified as: immune, plants without symptoms and negative serology; resistant, plants with mild mosaic and positive serology; susceptible, plants with mosaic and positive serology; and highly susceptible, plants with severe mosaic, other systemic symptoms, including systemic necrosis, and positive serology. Simple and multiple resistances to viruses were identified among the evaluated genotypes, but none of them showed multiple immunities to all isolates. Four genotypes showed immunity to all CPSMV isolates, two were immune to CABMV and two showed immunity to CMV. Eleven genotypes showed multiple resistances to two viruses, allowing for the development of new cultivars with more stable and broader resistance. Genotypes Purple Knuckle Hull-55, MNC-03-731C-21 and CNCx284-66E show resistance to CABMV, even when inoculated with CMV.

Buprenorphine and norbuprenorphine quantification in human plasma by simple protein precipitation and ultra-high performance liquid chromatography tandem mass spectrometry.

A highly sensitive ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method was developed for the quantification of buprenorphine and its major metabolite norbuprenorphine in human plasma. In order to speed up the process and decrease costs, sample preparation was performed by simple protein precipitation with acetonitrile. To the best of our knowledge, this is the first application of this extraction technique for the quantification of buprenorphine in plasma. Matrix effects were strongly reduced and selectivity increased by using an efficient chromatographic separation on a sub-2μm column (Acquity UPLC BEH C18 1.7μm, 2.1×50mm) in 5min with a gradient of ammonium formate 20mM pH 3.05 and acetonitrile as mobile phase at a flow rate of 0.4ml/min. Detection was made using a tandem quadrupole mass spectrometer operating in positive electrospray ionization mode, using multiple reaction monitoring. The procedure was fully validated according to the latest Food and Drug Administration guidelines and the Société Française des Sciences et Techniques Pharmaceutiques. Very good results were obtained by using a stable isotope-labeled internal standard for each analyte, to compensate for the variability due to the extraction and ionization steps. The method was very sensitive with lower limits of quantification of 0.1ng/ml for buprenorphine and 0.25ng/ml for norbuprenorphine. The upper limit of quantification was 250ng/ml for both drugs. Trueness (98.4-113.7%), repeatability (1.9-7.7%), intermediate precision (2.6-7.9%) and internal standard-normalized matrix effects (94-101%) were in accordance with international recommendations. The procedure was successfully used to quantify plasma samples from patients included in a clinical pharmacogenetic study and can be transferred for routine therapeutic drug monitoring in clinical laboratories without further development.

Acylation of chiral alcohols: a simple procedure for chiral GC analysis

The use of iodine as a catalyst and either acetic or trifluoroacetic acid as a derivatizing reagent for determining the enantiomeric composition of acyclic and cyclic aliphatic chiral alcohols was investigated. Optimal conditions were selected according to the molar ratio of alcohol to acid, the reaction time, and the reaction temperature. Afterwards, chiral stability of chiral carbons was studied. Although no isomerization was observed when acetic acid was used, partial isomerization was detected with the trifluoroacetic acid. A series of chiral alcohols of a widely varying structural type were then derivatized with acetic acid using the optimal conditions. The resolution of the enantiomeric esters and the free chiral alcohols was measured using a capillary gas chromatograph equipped with a CP Chirasil-DEX CB column. The best resolutions were obtained with 2-pentyl acetates (α = 3.00) and 2-hexyl acetates (α = 1.95). This method provides a very simple and efficient experimental workup procedure for analyzing chiral alcohols by chiral-phase GC.

Outcomes of minimally invasive simple prostatectomy for benign prostatic hyperplasia: a systematic review and meta-analysis.

PURPOSE: (1) To assess the outcomes of minimally invasive simple prostatectomy (MISP) for the treatment of symptomatic benign prostatic hyperplasia in men with large prostates and (2) to compare them with open simple prostatectomy (OSP). METHODS: A systematic review of outcomes of MISP for benign prostatic hyperplasia with meta-analysis was conducted. The article selection process was conducted according to the PRISMA guidelines. RESULTS: Twenty-seven observational studies with 764 patients were analyzed. The mean prostate volume was 113.5 ml (95 % CI 106-121). The mean increase in Qmax was 14.3 ml/s (95 % CI 13.1-15.6), and the mean improvement in IPSS was 17.2 (95 % CI 15.2-19.2). Mean duration of operation was 141 min (95 % CI 124-159), and the mean intraoperative blood loss was 284 ml (95 % CI 243-325). One hundred and four patients (13.6 %) developed a surgical complication. In comparative studies, length of hospital stay (WMD -1.6 days, p = 0.02), length of catheter use (WMD -1.3 days, p = 0.04) and estimated blood loss (WMD -187 ml, p = 0.015) were significantly lower in the MISP group, while the duration of operation was longer than in OSP (WMD 37.8 min, p < 0.0001). There were no differences in improvements in Qmax, IPSS and perioperative complications between both procedures. The small study sizes, publication bias, lack of systematic complication reporting and short follow-up are limitations. CONCLUSIONS: MISP seems an effective and safe treatment option. It provides similar improvements in Qmax and IPSS as OSP. Despite taking longer, it results in less blood loss and shorter hospital stay. Prospective randomized studies comparing OSP, MISP and laser enucleation are needed to define the standard surgical treatment for large prostates.

Copeptin is associated with kidney length, renal function, and prevalence of simple cysts in a population-based study.

Arginine vasopressin (AVP) has a key role in osmoregulation by facilitating water transport in the collecting duct. Recent evidence suggests that AVP may have additional effects on renal function and favor cyst growth in polycystic kidney disease. Whether AVP also affects kidney structure in the general population is unknown. We analyzed the association of copeptin, an established surrogate for AVP, with parameters of renal function and morphology in a multicentric population-based cohort. Participants from families of European ancestry were randomly selected in three Swiss cities. We used linear multilevel regression analysis to explore the association of copeptin with renal function parameters as well as kidney length and the presence of simple renal cysts assessed by ultrasound examination. Copeptin levels were log-transformed. The 529 women and 481 men had median copeptin levels of 3.0 and 5.2 pmol/L, respectively (P<0.001). In multivariable analyses, the copeptin level was associated inversely with eGFR (β=-2.1; 95% confidence interval [95% CI], -3.3 to -0.8; P=0.002) and kidney length (β=-1.2; 95% CI, -1.9 to -0.4; P=0.003) but positively with 24-hour urinary albumin excretion (β=0.11; 95% CI, 0.01 to 0.20; P=0.03) and urine osmolality (β=0.08; 95% CI, 0.05 to 0.10; P<0.001). A positive association was found between the copeptin level and the presence of renal cysts (odds ratio, 1.6; 95% CI, 1.1 to 2.4; P=0.02). These results suggest that AVP has a pleiotropic role in renal function and may favor the development of simple renal cysts.

A simple halide-to-anion exchange method for heteroaromatic salts and ionic liquids

A broad and simple method permitted halide ions in quaternary heteroaromatic and ammonium salts to be exchanged for a variety of anions using an anion exchange resin (A− form) in non-aqueous media. The anion loading of the AER (OH− form) was examined using two different anion sources, acids or ammonium salts, and changing the polarity of the solvents. The AER (A− form) method in organic solvents was then applied to several quaternary heteroaromatic salts and ILs, and the anion exchange proceeded in excellent to quantitative yields, concomitantly removing halide impurities. Relying on the hydrophobicity of the targeted ion pair for the counteranion swap, organic solvents with variable polarity were used, such as CH3OH, CH3CN and the dipolar nonhydroxylic solvent mixture CH3CN:CH2Cl2 (3:7) and the anion exchange was equally successful with both lipophilic cations and anions.