Determination of iodide by detection of iodine using gas-diffusion flow injection and chemiluminescence

This work describes development of a flow injection (FI) system for determination of iodide, based on the chemiluminescence (CL) reaction between iodine and luminol. Iodide in the sample zone is oxidized to iodine. Employment of a gas-diffusion (GD) unit allows for selective detection of the generated CL (425 nm). Preliminary results showed for concentrations of less than 2 mg L⁻¹, that signals were irreproducible and that the calibration was not linear.In order to solve these problems, a method of ‘membrane conditioning’ was investigated, in which iodide stream was continuously merged with oxidant to generate I₂ that conditioned the GD membrane and tubing. This minimized surface interaction between the active surface and the I₂ generated from the samples, thus improving both precision and sensitivity. By employing membrane conditioning, it has been possible to reliably detect concentrations down to 0.1 mg L⁻¹.At the optimized condition, an excellent linear calibration (r² = 0.999) was obtained from 0.1 to 1.0 mg L⁻¹. The method was successfully applied to determine iodide in some pharmaceutical products such as potassium iodide tablets and a liquid patent medicine. However, for vitamin tablets, ascorbic acid was found to interfere seriously by causing a negative signal.     

Simple in‐house flow‐injection capillary electrophoresis with capacitively coupled contactless conductivity method for the determination of colistin

An in‐house flow‐injection capillary electrophoresis with capacitively coupled contactless conductivity detection method was developed for the direct measurement of colistin in pharmaceutical samples. The flow injection and capillary electrophoresis systems are connected by an acrylic interface. Capillary electrophoresis separation is achieved within 2 min using a background electrolyte solution of 5 mM 2‐morpholinoethanesulfonic acid and 5 mM histidine (pH 6). The flow‐injection section allows for convenient filling of the capillary and sample introduction without the use of a pressure/vacuum manifold. Capacitively coupled contactless conductivity detection is employed since colistin has no chromophore but is cationic at pH 6. Calibration curve is linear from 20 to 150 mg/L, with a correlation coefficient (r²) of 0.997. The limit of quantitation is 20 mg/L. The developed method provides precision, simplicity, and short analysis time.     

Simple and fast analysis of iohexol in human serums using micro‐hydrophilic interaction liquid chromatography with monolithic column

A simple and rapid method based on micro‐liquid chromatography using a synthetic monolithic capillary column was developed for determination of iohexol in human serums, a marker to evaluate the glomerular filtration rate. A hydrophilic methacrylic acid‐ethylene dimethacrylate monolith provided excellent selectivity and efficiency for iohexol with separation time of 3 min using a mobile phase of 40:60 v/v 50 mM phosphate buffer pH 5/methanol. Four serum protein removal, methods using perchloric acid, 50% acetonitrile, 0.1 M zinc sulfate, and centrifuge membrane filter were examined. The method of zinc sulfate was chosen due to its simplicity, compatibility with the mobile phase system, nontoxicity, and low cost. Interday calibration curves were conducted over iohexol concentrations range of 2–500 mg/L (R² = 0.9997 ± 0.0001) with detection limit of 0.44 mg/L. Intra‐ and interday precisions for peak area and retention time were less than 2.8 and 1.4%, respectively. The method was successfully applied to serum samples with percent recoveries from 102 to 104. The method was applied to monitor released iohexol from healthy subject. Compared with the commercially available reversed‐phase high‐performance liquid chromatography method, the presented method provided simpler chromatogram, faster separation with higher separation efficiency and much lower sample and solvent consumption.     

Catalytic degradation of polyolefins over hexagonal mesoporous silica: Effect of aluminum addition

Degradations of polypropylene (PP) and polyethylene (PE) over pure hexagonal mesoporous silica and aluminum-containing hexagonal mesoporous silica catalysts were studied in a fixed bed catalytic reactor at 380 and 430 °C, respectively. The thermal and catalytic degradations of both PP and PE in liquid-phase-contact and vapor-phase-contact modes over pure hexagonal mesoporous silica had no significant effect on the product yields. The liquid products were widely distributed in hydrocarbons with boiling point ranges of 36–405 °C. By adding a small amount of aluminum to the hexagonal mesoporous material, aluminium-containing hexagonal mesoporous silica exhibited good performance in cracking heavy molecular weight hydrocarbons into light hydrocarbons. High liquid yields and less coke deposits were obtained in liquid-phase-contact reaction with increasing aluminum content. The liquid products were mainly composed of C₅–C₁₀ hydrocarbons with boiling points of 36–174 °C, and propene, butene, and butane were main components in gaseous products. The effect of degradation temperature was not observed on product yields though degradation rate of polyolefin into liquid products was faster. Conversely, in vapor-phase-contact reaction, an increase in gaseous yield was observed when increasing the amount of aluminum and temperature of the cracking reactor, while the residue yield remained constant.     

Significant enhancement of thermal stability in the non-oxidative thermal degradation of bisphenol-A/aniline based polybenzoxazine aerogel

Previously we reported synthesis of a new type of organic aerogel from phenolic resins called polybenzoxazines and their transformation into carbon aerogels. Here, we further investigate the thermal degradation behaviors of both bulk polybenzoxazines and polybenzoxazine aerogels using Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA)/FTIR, and gas chromatography/time of flight-mass spectroscopy (GC/TOF-MS). The activation energy (E_a) of the decomposition step was determined using the Kissinger method. It was found that the polybenzoxazine aerogels exhibit much higher degradation temperatures and char yields than the bulk. The decomposition temperatures at 10% weight loss and the char yields at 800 °C of the bisphenol-A/aniline based polybenzoxazine aerogel increased up to 24% and 97% higher, respectively, than the corresponding bulk values. Kinetic investigation indicated that the decomposition reaction of bulk polybenzoxazine exhibits three stages, whereas that of the polybenzoxazine aerogel features four stages with much higher overall activation energy. The enhanced thermal stability of the aerogel is ascribed to its highly porous structure, which increases the residence time of the primary decomposition products, and hence generates greater opportunity to form secondary reactions.     

Monolithic and packed particle materials for in-line pre-concentration in capillary electrophoresis for 4-hydroxy-3-methoxy-methamphetamine and terbutaline

In-line solid-phase extraction (SPE) for capillary electrophoresis (CE) was investigated using a synthesized monolith and a commercial packing material. Terbutaline (TER) and 4-hydroxy-3-methoxy-methamphetamine (HMMA) with benzyl alcohol as the electroosmotic flow marker were employed as model compounds. Two types of methacrylate-based monoliths, namely methacrylic acid-ethylene dimethacrylate and butylmethacrylate-ethylene dimethacrylate were examined. Preliminary results indicated that a non-aqueous separating medium is more suitable for these methacrylate monoliths than a purely aqueous medium (non-reproducible elution). However, coupling of the methacrylic acid-ethylene dimethacrylate with non-aqueous capillary electrophoresis could not provide good precision for the three model compounds. A packed-silica C18 SPE was also adopted by simply packing the C18 particles in situ in the separation capillary. Using an aqueous running buffer (10 mM phosphate buffer (PPB), pH 7), acceptable precision could be obtained with this type of SPE material. With a 10 min loading time and 20 min total analysis time, the pre-concentration factors were 333 and 1000 for TER and HMMA, respectively. The %RSD were less than 4.5 and 0.3 for the peak areas and migration times, respectively, for both HMMA and TER (n=20).     

Separation of alpha-, beta-, gamma-, delta-tocopherols and alpha-tocopherol acetate on a pentaerythritol diacrylate monostearate-ethylene dimethacrylate monolith by capillary electrochromatography

This work reports the first use of a monolith with method development for the separation of tocopherol (TOH) compounds by CEC with UV detection. A pentaerythritol diacrylate monostearate-ethylene dimethacrylate (PEDAS-EDMA) monolithic column has been investigated for an optimised condition to separate alpha-, beta-, gamma- and delta-TOHs, and alpha-tocopherol acetate (TAc). The PEDAS-EDMA monolith showed a remarkably good selectivity for separation of the TOH isomers including the beta- and gamma-isomers which are not easily separated by standard C8 or C18 particle-packed columns. Retention studies indicated that an RP mechanism was involved in the separation on the PEDAS-EDMA column, but polar interactions with the underlying ester and hydroxyl groups enhanced the separation of the problematic beta- and gamma-isomers. Separation of all the compounds was achieved within 25 min using 3:10:87 v/v/v 100 mM Tris buffer (pH 9.3)/methanol/ACN as the mobile phase. The method was successfully applied to a pharmaceutical sample with recoveries from 93 to 99%. Intraday and interday precisions (%RSD) for peak area and retention time were less than 2.3. LODs for all four TOHs and TAc were below 1 ppm.     

Porous structure of polybenzoxazine-based organic aerogel prepared by sol–gel process and their carbon aerogels

New organic aerogels were successfully prepared from a new class of phenolic resins called polybenzoxazines synthesized via conventional thermal curing reaction of a benzoxazine monomer using xylene as a solvent. Without the need for using supercritical conditions to remove the solvent during the process, the carbon aerogels were obtained with a much shortened time. From two different concentrations of benzoxazine solution, 20 and 40 wt%, the resulting polybenzoxazine aerogels, having densities of 260 and 590 kg/m³, respectively, were obtained after the curing process. The subsequent carbon aerogels were prepared by the carbonization of polybenzoxazine aerogels. The corresponding carbon aerogels exhibited a microporous structure with pore diameters less than 2 nm, the densities of 300 and 830 kg/m³, and surface area of 384 and 391 m²/g, respectively. The texture of the carbon aerogels was denser than that of their organic aerogel precursor, as evidenced by scanning electron microscopy. The transformation of the polybenzoxazine aerogel to the carbon aerogel was clearly observed using fourier transform infrared spectroscopy.     

Comparative potentiality of Kans grass (Saccharum spontaneum) and Giant reed (Arundo donax) as lignocellulosic feedstocks for the release of monomeric sugars by microwave/chemical pretreatment

Two-stage microwave (microwave/NaOH pretreatment followed by microwave/H₂SO₄ pretreatment) was used to release monomeric sugars from Kans grass (Saccharum spontaneum) and Giant reed (Arundo donax). The optimum pretreatment conditions were investigated, and the maximum monomeric sugar yields were compared. The microwave-assisted NaOH and H₂SO₄ pretreatments with a 15:1 liquid-to-solid ratio were studied by varying the chemical concentration, reaction temperature, and reaction time to optimize the amount of monomeric sugars. The maximum amounts of monomeric sugars released from microwave-assisted NaOH pretreatment were 6.8 g/100 g of biomass [at 80 °C/5 min, 5 % (w/v) NaOH for S. spontaneum and at 120 °C/5 min, 5 % (w/v) NaOH for A. donax]. Furthermore, the maximum amounts of monomeric sugars released from microwave-assisted H₂SO₄ pretreatment of S. spontaneum and A. donax were 33.8 [at 200 °C/10 min, 0.5 % (w/v) H₂SO₄] and 31.9 [at 180 °C/30 min, 0.5 % (w/v) H₂SO₄] g/100 g of biomass, respectively. The structural changes of S. spontaneum and A. donax were characterized using Fourier transform infrared spectroscopy and scanning electron microscopy.     

Synthesis and characterization of M-MCM-48 (M = Cr,Ce) from silatrane via sol–gel process

Chromium and cerium incorporated into MCM-48 framework are hydrothermally synthesized via sol–gel process without any additives and characterized by X-ray diffraction, N₂ adsorption/desorption, Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Diffuse reflectance UV–vis spectroscopy, and Thermogravimetric analysis. Results indicate that the materials possess a long-range ordered structure, high specific surface area, and narrow pore size distribution. SEM images illustrate the edge-truncated octahedron morphology of Cr-MCM-48 while Ce-MCM-48 preserves the truncated octahedron of the MCM-48 parent material. TEM images show the pore network of Ia3d symmetry after loading metals. Spectroscopic data confirm the existence of metals in the framework and extra-framework. At low Cr content, Cr-MCM-48 contains only Cr(VI) species while rich Cr content loading results in both the Cr(VI) and Cr(III) species. The hydrothermal stability of MCM-48 is enhanced by carefully incorporating metals into the parent material.