Environmental Benign Catalysis for Linear Alkylbenzene Synthesis: A Review

In this review, we discuss the recent advances in both of non-zeolitic and zeolitic solid acid catalysts for linear alkylbenzene (LAB) synthesis with special focus on improvements of 2-LAB isomer selectivity and catalyst stability. Effects of post treatment methods particularly dealumination and desilication on the catalytic performance of mordenite in terms of mesoporosity, diffusivity and deactivation mechanism are extensively reviewed. Perspective trends in the development of mesoporous zeolites for LAB synthesis are also presented.     

Analysis of steroids in yeast-mediated cell culture by on-line solid-phase extraction coupled high-performance liquid chromatography electrospray-ionization/mass spectrometry and novel continuous postcolumn infusion of internal standard technique

The reduction of 17-ketosteroid estrone or androstenedione to corresponding 17α- and 17β-estradiol or testosterone and epitestosterone has been performed with Saccharomyces cerevisiae. In the analysis of the cell culture, the solid-phase extraction (SPE) method was on-line coupled to high-performance liquid chromatography electrospray-ionization/mass spectrometry (HPLC-ESI/MS) for sample pretreatment to eliminate the complicated matrix interference and preconcentrate of the analytes before chromatographic separation. A novel quantification method with the continuous postcolumn infusion of internal standard was developed for the determination of substrate and products. This novel quantitative method can stabilize and enhance the ionization of all analytes during analysis. The HPLC-ESI/MS analysis of estrone, 17α-, and 17β-estradiol was operated with a negative ion mode and the analysis of androstenedione, testosterone, and epitestosterone was operated with a positive ion mode. The optimal concentration of the internal standard progesterone with the continuous postcolumn infusion technique was 3 μg mL⁻¹ for estrogen analysis and 1 ng mL⁻¹ for androgen analysis and both were at a constant infusion rate of 0.5 μL min⁻¹. All of the linear correlation coefficients of the standard calibration curves were over 0.99 and had a linear range from 0 to 50 ng mL⁻¹. The limit of detections (LODs) and the limit of quantitations (LOQs) for steroids analyzed were from 0.12 to 0.36 ng mL⁻¹ and from 0.4 to 1.2 ng mL⁻¹, respectively. The analysis accuracies and precisions were better than 94% and lower than 8.8% R.S.D., respectively. The developed method for the analysis of steroids in the cell culture was successful.     

Energy transfer of highly vibrationally excited phenanthrene and diphenylacetylene

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold phenanthrene and diphenylacetylene in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer between naphthalene and Kr, energy transfer between phenanthrene and Kr shows a larger cross-section for vibrational to translational (V → T) energy transfer, a smaller cross-section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation. These differences are further enlarged in the comparison between naphthalene and diphenylacetylene. In addition, less complex formation and significant increases in the large V → T energy transfer probabilities, termed supercollisions in diphenylacetylene and Kr collisions were observed. The differences in the energy transfer between these highly vibrationally excited molecules are attributed to the low-frequency vibrational modes, especially those vibrations with rotation-like wide-angle motions.     

Preparation of carbon fibers/carbon/alumina tubular composite membranes and their applications in treating Cu-CMP wastewater by a novel electrochemical process

In this study, the alumina substrate was first prepared by the extrusion method, then followed by poly-vinylydenchloride (PVDC) film wrapping, PVDC carbonization, catalyst precursor coating, and the chemical vapor deposition (CVD) process to grow carbon fibers on the carbon interlayer. The carbon fibers/carbon/alumina tubular composite membranes (CCA-TCMs) thus obtained, with a pore size distribution ranging from 2 to 10 nm, were further characterized by scanning electron microscopy, transmission electron microscopy, and permporometry. A prepared CCA-TCM of this kind was incorporated into a novel simultaneous crossflow electrocoagulation and electrofiltration (EC/EF) treatment module to evaluate its capability in treating Cu-CMP (chemical mechanical polishing) wastewater. Crossflow EC/EF performance tests were carried out based on the 2³⁻¹ fractional factorial design using the electric field strength, crossflow velocity, and transmembrane pressure (TMP) as the experimental factors. Under the optimal operating conditions, the CCA-TCM associated EC/EF treatment module is capable of treating Cu-CMP wastewater in a proper manner. Permeate thus obtained had a turbidity of below 1 NTU and the removal efficiencies of total solids content, total organic carbon, copper, and silicon for Cu-CMP wastewater were 72%, 81%, 92%, and 87%, respectively.     

A comparative study of gold nanocubes, octahedra, and rhombic dodecahedra as highly sensitive SERS substrates

Gold nanocubes, octahedra, and rhombic dodecahedra with roughly two sets of particle sizes have been successfully synthesized via a seed-mediated growth approach. All six samples were analyzed for comparative surface-enhanced Raman scattering (SERS) activity. All of these Au nanostructures were found to yield strong enhancement at a thiophenol concentration of 10(-7) M and are excellent SERS substrates. Rhombic dodecahedra with a rhombus edge length of 32 nm showed significantly better enhancement than the other samples and can reach a detection limit of 10(-8) M. Simulations of the binding energies of thiophenol on the different faces of gold and electric near-field intensities of these nanocrystals have been performed to evaluate the experimental results. Superior SERS activity of these nanocrystals can be expected toward the detection of many other molecules.     

Fabrication of single crystal CuGaS2 nanorods by X-ray irradiation

CuGaS(2) nanorods were synthesized by irradiating the precursor solution with intense X-rays. The products are single crystal nanorods with preferential [220] growth and a uniform size distribution. We also report on the photoresponse of drop-cast films of these nanorods.     

A practical synthesis of zanamivir phosphonate congeners with potent anti-influenza activity

Two phosphonate compounds 1a (4-amino-1-phosphono-DANA) and 1b (phosphono-zanamivir) are synthesized and shown more potent than zanamivir against the neuraminidases of avian and human influenza viruses, including the oseltamivir-resistant strains. For the first time, the practical synthesis of these phosphonate compounds is realized by conversion of sialic acid to peracetylated phosphono-DANA diethyl ester (5) as a key intermediate in three steps by a novel approach. In comparison with zanamivir, the high affinity of 1a and 1b can be partly attributable to the strong electrostatic interactions of their phosphonate groups with the three arginine residues (Arg118, Arg292, and Arg371) in the active site of neuraminidases. These phosphonates are nontoxic to the human 293T cells; they protect cells from influenza virus infection with EC(50) values in low-nanomolar range, including the wild-type WSN (H1N1), the 2009 pandemic (H1N1), the oseltamivir-resistant H274Y (H1N1), RG14 (H5N1), and Udorn (H3N2) influenza strains.     

Large-scale plasmonic microarrays for label-free high-throughput screening

Microarrays allowing simultaneous analysis of thousands of parameters can significantly accelerate screening of large libraries of pharmaceutical compounds and biomolecular interactions. For large-scale studies on diverse biomedical samples, reliable, label-free, and high-content microarrays are needed. In this work, using large-area plasmonic nanohole arrays, we demonstrate for the first time a large-scale label-free microarray technology with over one million sensors on a single microscope slide. A dual-color filter imaging method is introduced to dramatically increase the accuracy, reliability, and signal-to-noise ratio of the sensors in a highly multiplexed manner. We used our technology to quantitatively measure protein-protein interactions. Our platform, which is highly compatible with the current microarray scanning systems can enable a powerful screening technology and facilitate diagnosis and treatment of diseases.     

Electrochemical detection of propofol at the preanodized carbon electrode

Preanodized screen printed carbon electrode (SPCE) has been utilized for the detection of propofol. Here the preanodized SPCE possess the specific functional groups which help the detection and determination of propofol. The proposed SPCE shows a clear oxidation peak for the detection of propofol in pH 7.0 phosphate buffer solutions. Interestingly, it shows a well-defined individual oxidation peak for the detection of propofol in the presence interferences (mixture of ascorbic acid, dopamine, and uric acid). This type of pretreated SPCE successfully enhances the electrooxidation current and overcomes the interference effects and clearly exhibits the signals for the propofol detection using cyclic voltammetry and flow injection analysis techniques. The preanodized SPCE shows the electrooxidation signals for the propofol detection in the linear range of 0.09 to 0.90 μM, respectively. Further, the sensitivity of the proposed electrode for the propofol detection is found to be 3.6 μA μM⁻¹.     

Evaluation of runaway thermal reactions of di-<Emphasis Type=Italic>tert</Emphasis>-butyl peroxide employing calorimetric approaches

Di-tert-butyl peroxide (DTBP) is an organic peroxide (OP) which has widespread use in the various chemical industries. In the past, thermal runaway reactions of OPs have been caused by their general thermal instability or by reactive incompatibility in storage or operation, which can create potential for thermal decomposition reaction. In this study, differential scanning calorimetry was applied to measure the heat of decomposition reactions, which can contribute to understand the reaction characteristics of DTBP. Vent sizing package 2 was also employed to evaluate rates of increase for temperature and pressure in decomposition reactions, and then the thermokinetic parameters of DTBP were estimated. Finally, hazard characteristics of the gassy system containing DTBP, specifically with respect to thermal criticality, were clearly identified.