Highly sensitive and selective dopamine detection by an amperometric biosensor based on tyrosinase/MWNT/GCE

Dopamine (3,4-dihydroxylphenyl ethylamine) is the most significant neurotransmitter in the human nervous system. Abnormal dopamine levels cause fatal neurological disorders, and thus measuring dopamine level in actual samples is important. Although electrochemical methods have been developed for detecting dopamine with high accuracy, certain substances (e.g., ascorbic acid) in actual samples often interfere with electrochemical dopamine detection. We developed tyrosinase-based dopamine biosensor with high sensitivity and selectivity. An electrochemically pretreated tyrosinase/multi-walled carbon nanotube-modified glassy carbon electrode (tyrosinase/MWNT/GCE) was prepared as an amperometric biosensor for selective dopamine detection. For optimizing the biosensor performance, pH, temperature, and scan rate were investigated. The electrochemically pretreated tyrosinase/MWNT/GCE exhibited not only the highest sensitivity (1,323 mAM^?1 cm^?2) compared to previously reported tyrosinase-based dopamine sensors, but also good long-term stability, retaining 90% of initial activity after 30 days. Additionally, ascorbic acid, a major interfering substances, was not oxidized at the potential used to detect dopamine oxidation, and the interfering effect of 4mM ascorbic acid was negligible when monitoring 1mM dopamine. Consequently, the electrochemically pretreated tyrosinase/MWNT/GCE is applicable for highly selective and sensitive dopamine detection in actual samples including interfering substances, thereby extending the practical use to monitor and diagnose neurological disorders.     

Synthesis,Characterization and Catalytic Activities of Palladium(II) Nitroaryl Complexes

Two palladium(II) nitroaryl complexes trans-[bromo(p-nitrophenyl)bis(triphenylphosphine)palladium(II)] 1 and trans-[bromo(2,4-dinitrophenyl)bis(triphenylphosphine)palladium(II)] 2 have been synthesized. The complexes were characterized by FTIR and NMR (¹H, ¹³C and ³¹P) spectroscopy and elemental analysis. The molecular structure of complex 2, as confirmed by X-ray crystallography, reveals that the Pd atom and its neighboring groups (two PPh₃, Br and phenylene group) lie in a slightly distorted square plane. In the UV–Vis spectra of the complexes 1 and 2, the palladium to aryl charge transfer bands were observed. The emission peaks from the singlet excited states (S₁ → S₀) were observed in the photoluminescence spectra of the complexes. The thermal stability of the complexes has been studied by thermal gravimetric analysis (TGA). TGA data showed that both complexes are thermally stable up to 200 °C, and complex 1 is more stable than 2. The catalytic efficiency of the new palladium(II) complexes was studied as demonstrated using the Sonogashira coupling reactions with good yields. The experimental results suggest that the Sonogashira coupling reactions can be performed at moderate temperature (50 °C) using these new palladium(II) complexes as catalysts.     

Structural Control of NiO–YSZ/LSCF–YSZ Dual‐Layer Hollow Fiber Membrane for Potential Syngas Production

The objective of this study was to fabricate dual‐layer hollow fiber as a microreactor for potential syngas production via phase inversion‐based co‐extrusion/cosintering process. As the main challenge of phase inversion is the difficulty to obtain defect‐free fiber, this work focuses on the effect of the fabrication parameters, that is, nonsolvent content, sintering temperature and outer‐layer extrusion rate, on the macrostructure of the produced hollow fiber. SEM images confirm that the addition of nonsolvent has successfully minimized the finger‐like formation. At high sintering temperature, more dense hollow fiber was formed while outer‐layer extrusion rate affects the outer layer thickness.     

Comparison of different extraction methods for the extraction of major bioactive flavonoid compounds from spearmint (Mentha spicata L.) leaves

Different bioactive flavonoid compounds including catechin, epicatechin, rutin, myricetin, luteolin, apigenin and naringenin were obtained from spearmint (Mentha spicata L.) leaves by using conventional soxhlet extraction (CSE) and supercritical carbon dioxide (SC-CO₂) extraction at different extraction schemes and parameters. The effect of different parameters such as temperature (40, 50 and 60 °C), pressure (100, 200 and 300 bar) and dynamic extraction time (30, 60 and 90 min) on the supercritical carbon dioxide (SC-CO₂) extraction of spearmint flavonoids was investigated using full factorial arrangement in a completely randomized design (CRD). The extracts of spearmint leaves obtained by CSE and optimal SC-CO₂ extraction conditions were further analyzed by high performance liquid chromatography (HPLC) to identify and quantify major bioactive flavonoid compounds profile. Comparable results were obtained by optimum SC-CO₂ extraction condition (60 °C, 200 bar, 60 min) and 70% ethanol soxhlet extraction. As revealed by the results, soxhlet extraction had a higher crude extract yield (257.67 mg/g) comparing to the SC-CO₂ extraction (60.57 mg/g). Supercritical carbon dioxide extract (optimum condition) was found to have more main flavonoid compounds (seven bioactive flavonoids) with high concentration comparing to the 70% ethanol soxhlet extraction (five bioactive flavonoids). Therefore, SC-CO₂ extraction is considered as an alternative process compared to the CSE for obtaining the bioactive flavonoid compounds with high concentration from spearmint leaves.     

Prospects of non-catalytic supercritical methyl acetate process in biodiesel production

Conventional biodiesel production methods utilize alcohol as acyl acceptor and produces glycerol as side product. Hence, with escalating production of biodiesel throughout the world, it leads to oversupply of glycerol and subsequently causes devaluation in the market. In this study, methyl acetate was employed as acyl acceptor in non-catalytic supercritical methyl acetate (SCMA) process to produce fatty acid methyl esters (FAME) and side product of triacetin, a valuable fuel additive instead of glycerol. Consequently, the properties of biodiesel produced (FAME and triacetin) are superior compared to conventional biodiesel method (FAME only). In this research, the effects of reaction temperature, reaction time and molar ratio of methyl acetate to oil on the yield of biodiesel were investigated. Apart from that, the influence of impurities commonly found in waste oils/fats such as free fatty acids and water were studied as well and compared with methanol-based reactions of supercritical and heterogeneous catalysis. Results show that biodiesel yields in SCMA process could achieve 99 wt.% when the operating conditions were fixed at 400 °C/220 bar for reaction temperature, methyl acetate/oil molar ratio of 30:1 and 60 min of reaction time. Furthermore, SCMA did not suffer from adverse effect with the presence of impurities, proving that SCMA has a high tolerance towards contamination which is crucial to allow the utilization of inexpensive waste oils/fats as biodiesel feedstock.     

Improved selectivity in discriminating handedness and diameter of single-walled carbon nanotubes with N-substituted 3,6-carbazolylene-bridged chiral diporphyrin nanotweezers

Chiral diporphyrin nanotweezers 1 consisting of two chiral porphyrins with N-substituted 3,6-carbazolylene in between have been studied for the separation of single-walled carbon nanotubes (SWNTs). As compared to the analogous nanotweezers 2 without an N-substitutent, nanotweezers 1 with the N-octylcarbazolylene spacer exhibit much higher extraction ability and better selectivity for SWNTs. A narrower diameter range of SWNTs, from 0.88 to 0.92 nm, was selectively extracted with nanotweezers 1. In addition, only (7,6)-SWNTs of 0.90 nm diameter were optically enriched through extraction with 1, while SWNTs extracted with 2 showed lower optical purity of (7,6)-SWNTs. These enhanced extraction and discrimination abilities of 1 can be attributed to the formation of a more stable SWNT complex of 1 than of 2 in methanol.     

Regioselective Alkoxylation of 2,2,4-Trimethyl-1,3-pentanediol

An efficient procedure for the regioselective synthesis of secondary alcohol alkoxylates from 2,2,4-trimethyl-1,3-pentanediol (TMPD) is described. TMPD was reacted with propylene oxide followed by ethylene oxide in the presence of a catalytic amount of alkali metal hydroxide to form secondary alcohol alkoxylates. Instead of a mixture of compounds resulting from the reaction of TMPD and propylene oxide, the primary hydroxyl group of the TMPD reacted to form predominantly 2,2,4-trimethyl-3-hydroxypentylpropoxylate as the major product. On further ethoxylation the less hindered secondary hydroxyl group of the 2,2,4-trimethyl-3-hydroxypentylpropoxylate reacted predominantly. ¹³C NMR indicated that the secondary hydroxyl group (96.2 mol%) of TMPD remained unreacted during alkoxylation.     

Waterborne polysiloxane–urethane–urea for potential marine coatings

Waterborne polysiloxane–urethane–ureas (WBPSUU) were prepared through a prepolymer process using siloxane polyol, namely polydimethylsiloxane (PDMS) and polyether polyol, namely poly(tetramethyleneoxide glycol) (PTMG) as the soft segments. The goal of this study was to explore the potential use of polysiloxane–urethane–urea in marine coatings in order to boost the flexibility, adhesion, erosion, and foul-release property with respect to PDMS/PTMG ratio (PDMS wt%). The structural elucidation of the synthesized waterborne polyurethane and WBPSUU was carried out by FTIR, ¹H NMR, and ²⁹Si NMR spectroscopic techniques. The XPS and AFM analyses indicate that the polymer surface can be silicone enriched with the optimum PDMS content (15.76 wt%). The antifouling property of the coatings was investigated by the immersion test under a marine environment for 90 days. The fouled area was calculated for all the samples and the fouled area (%) decreased with increasing PDMS content. After 90 days the lowest fouled area (5%) was observed in the sample using WBPSUU4 (PDMS 15.76 wt%) among all of the samples.     

Development of coating materials from liquid wax esters for wood top-based coating

Of late, UV-curable products are gaining attention in the wood industry because of the effectiveness and efficiency of this method. UV-curable surface coatings are widely used because of their excellent properties and because they are environmentally friendly products. In this study, immobilized Candida antarctica lipase B was used to catalyze formation of liquid wax esters, such as adipate esters, via a solvent-free process. The adipate esters formed were then used as UV-curable reactants in the wood coating formulations, consisting of epoxy acrylate, additives, and a photoinitiator. The performance of the products was evaluated by coating them onto glass tiles (using gel content, hardness, and scratch resistance tests) and wood panels (using adhesion, impact, and heat resistance tests). The coated film from this formulation performed well during the evaluation tests. The gel content exhibited more than 90% polymerization, while the pendulum hardness gave a value of 55.25%. Both analyses were significant in determining the effect of irradiation cycles. A scratch test was also carried out to verify the resistance of the coating. The maximum weight load which can be resisted by the wax esters formulation is 4.5 N.     

Monomer sequence of partially hydrolyzed poly(4-tert-butoxystyrene) and morphology of diblock copolymers composing this polymer sequence as one block

The molecular characteristics of poly(4-tert-butoxystyrene) (O) upon hydrolysis reaction were investigated. It is known that O can be converted into poly(4-hydroxystyrene) (H) through hydrolysis reaction using strong acid. In this study, a set of poly(4-tert-butoxystyrene-co-4-hydroxystyrene)s (O/H copolymers) having various conversion rates, f_Hs, were prepared. Hydrolysis reaction is found to occur uniformly by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) where the average f_H obtained was consistent with that from ¹H NMR though a certain distribution in the number of hydrolyzed units was conceived. Monomer sequence of O/H copolymers was determined by ¹³C NMR and the changes in triad concentration were obtained by spectra subtraction method. As a result, ¹³C NMR reveals that O and H are statistically distributed. To evaluate the effect of hydrolysis on microphase-separated structure, we observed the morphology of partially hydrolyzed poly(4-tert-butylstyrene-block-4-tert-butoxystyrene) (BO) by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Samples with f_H from 0.21 to 0.67 form both lamellar (major component) and cylindrical (minor component) structures reflecting both the statistical manner of hydrolysis reaction and the possible localized distribution of H sequence.