Separation of crystal violet dyes and its application to pen ink analysis using CZE and MEKC methods

A crystal violet (CV) standard was irradiated under a Hg-Cd lamp for different exposure times to obtain various N-demethylation products. CZE effectively separated the photodegradation products based on molecular weight differences. In contrast, micellar EKC (MEKC), using SDS as the surfactant, was ineffective because the binding constants of the demethylation products and SDS were too close for separation. Nevertheless, MEKC analysis of ink has applications in forensic science because MEKC separated neutral components in the inks. Thus, MEKC can be used to obtain an ink "fingerprint" since each ink is unique depending on the location and time it was made. In contrast, CZE is useful for dating inks because CV is the primary ink dye and it photodegrades slowly.     

Polymer Coated Piezoelectric Quartz Crystal Protein Bio‐Sensors

A polymer coated piezoelectric crystal detection system with a home‐made computer interface for signal acquisition and data processing was prepared as a liquid chromatographic detector for various proteins. Various polymers, e.g., polyvinyl aldehhyde (polyacrolein) (PVA), polyacrylamide/glutaldehyde (PAA/GA) and bio‐gel A, were used as coating materials on quartz crystals for adsorption of various protein molecules, e.g., catalase (CA), hemoglobin (Hb), α‐chymotrypsin (Ch), albumin (Ab). The frequency responses of the polyacrlein coated piezoelectric detector for various proteins were in the order: catalase> hemoglobin> α‐chymotrypsin > albumin. In contrast, the order of the frequency responses of bio‐gel A and polyacrylamide/glutaldehyde coated piezoelectric crystals for these proteins were: hemoglobin> catalase > α‐chymotrypsin ≥ albumin and hemoglobin > albumin > catalase. The polyacrolein coated piezoelectric crystal protein detector exhibited a good linear frequency response with a high sensitivity of about 2.5×10³ Hz/(mg/mL) for catalase. In addition, bio‐gel A and polyacrylamide/glutaraldehyde coated crystals were sensitive to hemoglobin with sensitivities of about 4.5×10³ Hz/(mg/mL) and 3.0×10³ Hz/(mg/mL), respectively. Study of the interference of various organic molecules, e.g., alcohols, amines, ketones and carboxylic acids, in the detection of proteins with theses polymer coated crystals was also made. The polyacrolein coated crystal for proteins under went less interference from various organic molecules than bio‐gel A or polyacrylamide/glutaraldehyde coated crystals. Effects of coating load, concentration of proteins and flow rate of liquid chromatographic eluent were also investigated and discussed.     

Phase‐separated,conducting composites from polyaniline and benzobisthiazole rigid‐rod polymer

As an alternative method for processing polyaniline (PANI) from its conducting (protonated) state, vacuum casting of PANI from a methanesulfonic acid (MSA) solution provided films with electrical conductivity values of about 130–150 S/cm. In addition, we similarly prepared blended films of PANI · MSA and poly(p‐phenylene benzobisthiazole) (PBZT). This process eliminated the need for a subsequent protonation step and had the additional advantage that the conjugated PBZT may provide alternative conducting pathways. Conductivity values of the composite films ranged from 100 pS/cm to 124 S/cm, and the films displayed critical concentration behavior with a PANI threshold concentration of 2.75% and a critical exponent of 4. Transmission electron micrographs displayed phase‐separated regions with PANI forming a continuous network at high concentrations. Thermogravimetric analysis results demonstrated the thermal and thermooxidative stability advantage of the blends due to the PBZT component. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2539–2548, 2001     

Ferromagnetism study of Co<Subscript>0.2</Subscript>Mg<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>0.8−<Emphasis Type="Italic">x</Emphasis></Subscript>O films prepared by the sol–gel method

Co_0.2Mg _x Zn_0.8−x O films prepared with different molar ratio of magnesium acetate to zinc acetate were deposited on substrates by the sol–gel technique. X-ray diffraction, photoluminescence (PL) and ferromagnetism measurements were used to characterize the Co_0.2Mg _x Zn_0.8−x O diluted magnetic semiconductors. The acceptor-like defects were determined in the PL band and the intensity of the acceptor-related PL increased with increasing Mg concentration. Therefore, an increase in the number of the acceptor-like defects (zinc vacancies especially) in the Co_0.2Mg _x Zn_0.8−x O film may lead to the enhancement of the magnetic properties. It is worth noting that changes in Mg concentration and the number of the acceptor-like defects are important issues for producing strong ferromagnetism Co_0.2Mg _x Zn_0.8−x O films prepared by the sol–gel method.     

Determination of glucose and ethanol after enzymatic hydrolysis and fermentation of biomass using Raman spectroscopy

Raman spectroscopy has been used for the quantitative determination of the conversion efficiency at each step in the production of ethanol from biomass. The method requires little sample preparation; therefore, it is suitable for screening large numbers of biomass samples and reaction conditions in a complex sample matrix. Dilute acid or ammonia-pretreated corn stover was used as a model biomass for these studies. Ammonia pretreatment was suitable for subsequent measurements with Raman spectroscopy, but dilute acid-pretreated corn stover generated a large background signal that surpassed the Raman signal. The background signal is attributed to lignin, which remains in the plant tissue after dilute acid pretreatment. A commercial enzyme mixture was used for the enzymatic hydrolysis of corn stover, and glucose levels were measured with a dispersive 785 nm Raman spectrometer. The glucose detection limit in hydrolysis liquor by Raman spectroscopy was 8 g L⁻¹. The mean hydrolysis efficiency for three replicate measurements obtained with Raman spectroscopy (86 ± 4%) was compared to the result obtained using an enzymatic reaction with UV-vis spectrophotometry detection (78 ± 8%). The results indicate good accuracy, as determined using a Student's t-test, and better precision for the Raman spectroscopy measurement relative to the enzymatic detection assay. The detection of glucose in hydrolysis broth by Raman spectroscopy showed no spectral interference, provided the sample was filtered to remove insoluble cellulose prior to analysis. The hydrolysate was further subjected to fermentation to yield ethanol. The detection limit for ethanol in fermentation broth by Raman spectroscopy was found to be 6 g L⁻¹. Comparison of the fermentation efficiencies measured by Raman spectroscopy (80 ± 10%) and gas chromatrography-mass spectrometry (87 ± 9%) were statistically the same. The work demonstrates the utility of Raman spectroscopy for screening the entire conversion process to generate lignocellulosic ethanol.     

Molecular dynamics simulations of fluid methane properties using ab initio intermolecular interaction potentials

Intermolecular interaction energy data for the methane dimer have been calculated at a spectroscopic accuracy and employed to construct an ab initio potential energy surface (PES) for molecular dynamics (MD) simulations of fluid methane properties. The full potential curves of the methane dimer at 12 symmetric conformations were calculated by the supermolecule counterpoise‐corrected second‐order Møller‐Plesset (MP2) perturbation theory. Single‐point coupled cluster with single and double and perturbative triple excitations [CCSD(T)] calculations were also carried out to calibrate the MP2 potentials. We employed Pople's medium size basis sets [up to 6‐311++G(3df, 3pd)] and Dunning's correlation consistent basis sets (cc‐pVXZ and aug‐cc‐pVXZ, X = D, T, Q). For each conformer, the intermolecular carbon–carbon separation was sampled in a step 0.1 Å for a range of 3–9 Å, resulting in a total of 732 configuration points calculated. The MP2 binding curves display significant anisotropy with respect to the relative orientations of the dimer. The potential curves at the complete basis set (CBS) limit were estimated using well‐established analytical extrapolation schemes. A 4‐site potential model with sites located at the hydrogen atoms was used to fit the ab initio potential data. This model stems from a hydrogen–hydrogen repulsion mechanism to explain the stability of the dimer structure. MD simulations using the ab initio PES show quantitative agreements on both the atom‐wise radial distribution functions and the self‐diffusion coefficients over a wide range of experimental conditions. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009     

New benzo[b]furans as electroluminescent materials for emitting blue light

[structure: see text] New functionalized mono- and bis-benzo[b]furan derivatives were synthesized and developed as blue-light emitting materials. They possessed a CN, CHO, CH=CHPh, CH=CPh(2), or CH=CHCOOH group at the C4-position. Two benzo[b]furan nuclei in bis-benzo[b]furan derivatives were connected by a divinylbenzene bridge. With good volatility and thermal stability, bis-benzo[b]furan 7a was fabricated as a device. It emitted blue light with brightness 53430 cd/m(2) (at 15.5 V) and high maximum external quantum efficiency 3.75% (at 11 V).     

Selective Transfer Hydrogenation and Hydrogenation of Ketones Using a Defined Monofunctional (P^N(Bn)^N(Bn)^P)–RuII Complex

A defined (P^N^N^P)–Ru complex possessing tertiary amines within the ligand backbone proved to be highly active both in transfer hydrogenations and hydrogenations of a variety of ketones. As compared to the existing catalytic systems, no bifunctional activation of H₂ or of the substrate by the metal center and a secondary amine within the ligand backbone is required to obtain high activities at catalyst loadings of down to 10 ppm.     

Cascade One‐Pot Synthesis of Orange‐Red‐Fluorescent Polycyclic Cinnolino[2,3‐f]phenanthridin‐9‐ium Salts by Palladium(II)‐Catalyzed C−H Bond Activation of 2‐Azobiaryl Compounds and Alkenes

Quaternary ammonium salts were synthesized in moderate to good yields through double oxidative C?H bond activation on azobenzenes. The mechanism of the highly regioselective reaction of 2‐azobiaryls with alkenes to give orange‐red‐fluorescent cinnolino[2,3‐f]phenanthridin‐9‐ium salts and 15H‐cinnolino[2,3‐f]phenanthridin‐9‐ium‐10‐ide is proposed to involve ortho C?H olefination of the 2‐azobiaryl compound with the alkene, intramolecular aza‐Michael addition, concerted metalation–deprotonation (CMD), reductive elimination, and oxidation.     

DNA‐Templated Copper Nanoprobes: Overview,Feature, Application,and Current Development in Detection Technologies

Metal nanoprobes have recently attracted board research interestinr their application in establishing sensing systems due to their unique optical, electrical, physical, and chemical properties. In comparison to gold and silver nanoprobes, analytical platform based on copper nanoprobes (Cu‐NPs) is still in the early stages of development. In this review, we focus on single‐stranded, and double‐stranded DNA capped Cu‐NPs sensing systems which have been designed for various analytes, including metal ions, anions, small molecules, biomolecules (DNA, RNA, and protein, etc.). In addition, the application of Cu‐NPs in biological labeling or bio‐imaging platforms has also been introduced and summarized.