Determination of 5-nitroindazole using silver solid amalgam electrode

Monatshefte für Chemie - Chemical Monthly - The voltammetric behavior of 5-nitroindazole was investigated at polished (p-AgSAE) and at mercury meniscus-modified (m-AgSAE) silver solid amalgam...     

Sonogashira alkynylation of unprotected 8-brominated adenosines and guanosines: fluorescence properties of compact conjugated acetylenes containing a purine ring

A practical Sonogashira alkynylation protocol for the preparation of 8-alkynylated adenosines and guanosines has been developed. Protection of the sugar hydroxyl substituents is not required; protection hinders the purification of these products. A preliminary fluorescent study is reported, which shows that the presence of a substituent on the phenylene ring influences the fluorescent properties considerably, an outcome that could be utilized in biological applications.     

Optimal volume-corrected laplace-metropolis method

The article provides a refinement for the volume-corrected Laplace-Metropolis estimator of the marginal likelihood of DiCiccioet al. The correction volume of probability α in DiCiccioet al. is fixed and suggested to take the value α=0.05. In this article α is selected based on an asymptotic analysis to minimize the mean square relative error (MSRE). This optimal choice of α is shown to be invariant under linear transformations. The invariance property leads to easy implementation for multivariate problems. An implementation procedure is provided for practical use. A simulation study and a real data example are presented.     

Flow injection system with in-line Winkler's procedure using 16-way valve and spectrofluorimetric determination of dissolved oxygen in environmental waters

Flow injection spectrofluorimetry with in-line Winklers procedure was developed for the dissolved oxygen (DO) determination. 2-Thionaphthol reacted with iodine produced by Winkler’s method to form fluorescence inactive disulfide compound. To automate the process completely, a 5-channel flow system with a newly designed 16-way valve was assembled. The system consisted of a dispersion coil (DC), a precipitate formation coil (PFC), a precipitate dissolving coil (PDC), and extraction coil (EC). A calibration can be constructed by using a standard iodine solution for dissolved oxygen. The calibration graph was linear over the range 1.2×10⁻⁴∼6.0×10⁻⁴ mol l⁻¹ iodine (1.96∼9.80 mg O l⁻¹)). The relative standard deviation (n=6) was below 0.3% for the 4×10⁻⁴ mol l⁻¹ iodine (6.27 mg O l⁻¹) determination. The sample throughput was 12/h.     

Enhancing chemical analysis with signal derivatization using simple available software packages

Derivative techniques for analytical signal processing are useful for solving some noise and signal resolution problems in various fields of study such as titrimetry, spectrophotometry, chromatography and electrochemistry. The broad use of these techniques, however, is often limited by costly inflexible built-in software packages in commercial analytical instruments. We propose here the application of commercial simple software packages such as Microsoft® Excel and Microcal Origin for signal smoothing and fitting, and for obtaining derivative analytical signals in batch and flow-based analyses, including potentiometric titration, spectrophotometry, chromatography, voltammetry and sequential injection analysis (SIA). The worldwide (especially Excel) software packages are easy-to-use for less experienced users and have also capabilities for advanced users, and therefore employing such packages can result in expansion of useful derivative techniques. We demonstrate application of the available package-aided derivative capabilities for enhancing some chemical analyses, including potentiometric acid–base titration, Bradford assay of protein, chromatographic separation of ajmaline and reserpine and anodic stripping voltammetry of copper. The derivative signals from smoothed and fitted curves offer better accuracy and precision, even for non-resolving peaks and tailing peaks. In some cases, the optimization of experimental conditions is not further required, which can lead to fast method development.     

A facile synthesis of (S)-gizzerosine, a potent agonist of the histamine H2-receptor

A simple and direct approach for the synthesis of (S)-gizzerosine, an amino acid responsible for the disease, black vomit, and a potent histamine H₂-receptor, has been developed in 10 steps and in 31% overall yield from l-aspartic acid. The key steps involved a two-carbon homologation of an l-aspartic acid semi-aldehyde and direct alkylation of unprotected histamine with a 6-hydroxynorleucine derivative.     

A simple flow injection-reduced volume column system for hemoglobin typing

A flow injection (FI)-reduced volume column system was developed for hemoglobin (Hb) typing to be used as an initial screening method for thalassemia. The column was packed with 140 μl diethylaminoethyl (DEAE)-Sephadex A-50 ion exchange beads. Hb can be separated using Tris–HCl buffer solution with pH gradient 8.5–6.5 and then monitored spectrophotometrically at 415 nm. The hemolysate of 40 blood samples from packed red cells were screened for thalassemia by determining the amount of HbA₂ and HbE present. The proposed system was able to predict positive test results from those samples with β, E-trait and EE homozygous thalassemia, Hb types that were independently identified following the conventional method at the hospital laboratory. Advantages of the proposed system over the conventional column technique include low amount of reagents and blood sample needed, short analysis time and low cost. Each analysis required only 80 μl of 50 times diluted packed cells, which is equivalent to 1.6 μl undiluted packed cells, and it can be completed in only 35 min. This simple FI-reduced volume column system was demonstrated to be an economic alternative system for Hb typing to initially screen some types of thalassemia such as β-trait, E-trait and EE-homozygous which are commonly found in Thailand.     

Flow injection dialysis for the determination of anions using ion chromatography

Flow injection dialysis (FID) coupling with ion chromatography (IC) is proposed for simultaneous determination of some anions (bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate). A standard or sample containing the anions is injected into a donor stream of a mixture (0.022 M Na(2)CO(3) and 0.028 M NaHCO(3)) flowing into a dialysis cell. The bolus of the dialysate containing the anions, in the acceptor stream of water, flows to the IC injection valve where a portion of the bolus is injected into the IC and analysed under normal IC conditions, with a conductivity detector. FID provides on-line separation and dilution of the analytes from matrix especially from some species such as proteins, surfactant, particulates which may cause damage to the IC columns. Prolongation of life-time of the IC columns is an additional advantage to others which will be discussed. On-line dialysis-IC was also investigated.     

Toward the synthesis of reidispongiolide a: stereocontrolled synthesis of the C17-C22 and C23-C35 degradation fragments

[structure: see text] By relying on the asymmetric aldol reactions of chiral ketones, a highly stereocontrolled synthesis of each of the C(17)-C(22) and C(23)-C(35) degradation fragments of reidispongiolide A has been achieved. This permits a configurational assignment of the complete C(17)-C(36) region of this antimitotic macrolide, along with providing advanced intermediates for a projected total synthesis.     

The effect of the “Inert” support on relative photocatalytic activity in the oxidative decomposition of alcohols on irradiated titanium dioxide composites

Reduced quantum efficiencies for the photocatalytic degradation of cyclohexanol, cyclododecanol, 2-hexanol, and benzyl alcohol are observed on TiO₂ particles included within small pore zeolitic supports suspended in acetonitrile. A modest reduction in photocatalytic activity observed with TiO₂ included within large pore zeolites and pillared clays is attributed to reflective and refractive losses of incident light. No appreciable substrate size selectivity could be observed in this series of supported TiO₂ composites. TS-1, a titanium-containing zeolite with Ti in tetrahedral lattice sites, was photoactive, although ETS-10, a titanium-containing zeolite with Ti in octahedral lattice sites, was less so. The low quantum yield residual photoactivity observed with these alcoholic substrates on unmodified zeolites may derive from surface charge transfer complexation, as suggested by diffuse reflectance absorption measurements.