Two independent molecules that differ in terms of rotation about the central S-N bond comprise the asymmetric unit of the title compound 1. The molecules have a V-shape with the dihedral angles between the fused ring system and benzene ring being 79.08(6)° and 72.83(5)°, respectively. The packing is mostly driven by p···p interactions occurring between the tolyl ring of one molecule and the C6 ring of the indole fused ring system of the other. DFT and IRC calculations for these and related 1-(arylsulfonyl)indole molecules showed that the rotational barrier about the S-N bond between conformers is within the 2.5-5.5 kcal/mol range. Crystal data for C16H13NO3S (1): Mr = 299.33, space group Pna21, a = 19.6152(4) Å, b = 11.2736(4) Å, c = 12.6334(3) Å, V = 2793.67(13) Å3, Z = 8, Z' = 2, R = 0.034.
Alkylbenzenes, molecular markers of sewage, were measured in 34 green mussels collected from India, Indonesia, Malaysia, Thailand, Cambodia, Vietnam, and the Philippines together with blue mussels collected from Tokyo Bay, Japan. Linear alkylbenzene (LAB) concentrations in South and South East Asian countries ranged from 10 to 1,640 ng-sigmaLAB/g-dry tissue. In some populous cities, LAB concentrations were similar or higher than those found in northern Tokyo Bay which is heavily impacted by sewage effluents. I/E ratios (a ratio of internal to external isomers of LABs) in the South and South East Asian countries (1-3) were much lower than those in Tokyo Bay (3-8), indicating sewage discharged in the coastal zone is poorly treated (e.g., raw sewage and/or primary effluents). Alkylbenzenes with branched alkyl chains, tetrapropylene-based alkylbenzenes, were also detected in mussels from Indonesia and Philippines. This "tell-tale" sign indicates that poorly degradable detergents are still in use in this area, although they have long been phased-out in many industrialized countries.
Pseudo-first-order rate constants (k(obs)) for alkaline hydrolysis of N-benzylphthalimide (1) show a nonlinear decrease with the increase in [C(m)E(n)]T (total concentration of Brij 58, m = 16, n = 20 and Brij 56, m = 16, n = 10) at constant [CH(3)CN] and [NaOH]. These nonionic micellar effects, within the certain typical reaction conditions, have been explained in terms of the pseudophase micellar (PM) model. The values of micellar binding constants (KS) of 1 are 1.04 x 10(3) M(-1) (at 1.0 x 10(-3) M NaOH) and 1.08 x 10(3) M(-1) (at 2.0 x 10(-3) M NaOH) for C(16)E(20) as well as 600 M(-1) (at 7.6 x 10(-4) M NaOH) and 670 M(-1) (at 1.0 x 10(-3) M NaOH) for C(16)E(10) micelles. The pseudo-first-order rate constants (kM) for hydrolysis of 1 in C(16)E(20) micellar pseudophase are approximately 90-fold smaller than those (kW) in water phase. The values of kM for hydrolysis of 1 in C(16)E(10) micelles are almost zero. Kinetic coupled with UV spectral data reveals significant irreversible nonionic micellar binding of 1 molecules in the micellar environment of nearly zero hydroxide ion concentration at >or=0.14 M C(16)E(20) and 1.0 x 10(-3) M NaOH while such observations could not be detected at or=3 x 10(-3) M C(16)E(10) and 7.6 x 10(-4) M NaOH, while the rate of hydrolysis of 1 is completely ceased at >or=0.05 M C(16)E(10) and 7.6 x 10(-4) M NaOH. The rate of hydrolysis of 1 at 5.0 x 10(-2) and 8.8 x 10(-2) M C(16)E(10) and 1.0 x 10(-3) M NaOH reveals the formation of presumably phthalic anhydride, whereas such observation was not observed in the C(16)E(20) micellar system under similar experimental conditions.
The present study investigated adsorptive removal of toluene and ethylbenzene from the aqueous media via using biochar derived from municipal solid waste (termed "MSW-BC") in a single and binary contaminant system at 25-45 °C. The adsorption was evaluated at different pH (3-10), experimental time (up to 24 h), and initial adsorbate concentrations (10-600 μg/L) in single and binary contaminant system. A fixed-bed column experiment was also conducted using MSW-BC (0.25%) and influent concentration of toluene and ethylbenzene (4 mg/L) at 2 mL/min of flow rate. The adsorption of toluene and ethylbenzene on the MSW-BC was mildly dependent on the pH, and the peak adsorption ability (44-47 μg/g) was recorded at a baseline pH of ~8 in mono and dual contaminant system. Langmuir and Hill are the models that match the isotherm results in a single contaminant environment for both toluene (R2 of 0.97 and 0.99, respectively) and ethylbenzene (R2 of 0.99 and 0.99, respectively) adsorption. In the binary system, the isotherm models matched in the order of Langmuir > Hill > Freundlich for toluene, whereas Hill > Freundlich > Langmuir for ethylbenzene. The adsorption in the batch experiment was likely to take place via cooperative and multilayer adsorption onto MSW-BC involving hydrophobic, π- π and n- π attractions, specific interaction such as hydrogen-π and cation-π interactions, and van der Waals interactions. The thermodynamic results indicate exothermic adsorption occurred by physical attractions between toluene and ethylbenzene, and MSW-BC. The breakthrough behavior of toluene and ethylbenzene was successfully described with Yoon-Nelson and Thomas models. The data demonstrate that the low-cost adsorbent derived from the municipal solid waste can be utilized to remove toluene and ethylbenzene in landfill leachate.
CO2 separation from CH4 by using mixed matrix membranes has received great attention due to its higher separation performance compared to neat polymeric membrane. However, Robeson's trade-off between permeability and selectivity still remains a major challenge for mixed matrix membrane in CO2/CH4 separation. In this work, we report the preparation, characterization and CO2/CH4 gas separation properties of mixed matrix membranes containing 6FDA-durene polyimide and ZIF-8 particles functionalized with different types of amine groups. The purpose of introducing amino-functional groups into the filler is to improve the interaction between the filler and polymer, thus enhancing the CO2 /CH4 separation properties. ZIF-8 were functionalized with three differents amino-functional group including 3-(Trimethoxysilyl)propylamine (APTMS), N-[3-(Dimethoxymethylsilyl)propyl ethylenediamine (AAPTMS) and N1-(3-Trimethoxysilylpropyl) diethylenetriamine (AEPTMS). The structural and morphology properties of the resultant membranes were characterized by using different analytical tools. Subsequently, the permeability of CO2 and CH4 gases over the resultant membranes were measured. The results showed that the membrane containing 0.5 wt% AAPTMS-functionalized ZIF-8 in 6FDA- durene polymer matrix displayed highest CO2 permeability of 825 Barrer and CO2/CH4 ideal selectivity of 26.2, which successfully lies on Robeson upper bound limit.
Sewage pollution is one of major concerns of coastal and shoreline settlements in Southeast Asia, especially Brunei. The distribution and sources of LABs as sewage molecular markers were evaluated in surface sediments collected from Brunei Bay. The samples were extracted, fractionated and analyzed using gas chromatography- mass spectrometry (GC-MS). LABs concentrations ranged from 7.1 to 41.3 ng g(-1) dry weight (dw) in surficial sediments from Brunei Bay. The study results showed LABs concentrations variably due to the LABs intensity and anthropogenic influence along Brunei Bay in recent years. The ratio of Internal to External isomers (I/E ratio) of LABs in sediment samples from Brunei Bay ranged from 0.56 to 2.17 along Brunei Bay stations, indicating that the study areas were receiving primary and secondary effluents. This is the first study carried out to assess the distribution and sources of LABs in surface sediments from Brunei Bay, Brunei.
This study aims to determine the composition of BTEX (benzene, toluene, ethylbenzene and xylene) and assess the risk to health at different sites in Malaysia. Continuous monitoring of BTEX in Kuala Lumpur City Centre, Kuala Terengganu, Kota Kinabalu and Fraser Hill were conducted using Online Gas Chromatograph. For comparison, BTEX at selected hotspot locations were determined by active sampling method using sorbent tubes and Thermal Desorption Gas Chromatography Mass Spectrometry. The hazard quotient (HQ) for non-carcinogenic and the life-time cancer risk (LTCR) of BTEX were calculated using the United States Environmental Protection Agency (USEPA) health risk assessment (HRA) methods. The results showed that the highest total BTEX concentrations using continuous monitoring were recorded in the Kuala Lumpur City Centre (49.56 ± 23.71 μg/m3). Toluene was the most dominant among the BTEX compounds. The average concentrations of benzene ranged from 0.69 ± 0.45 μg/m3 to 6.20 ± 3.51 μg/m3. Measurements using active sampling showed that BTEX concentrations dominated at the roadside (193.11 ± 114.57 μg/m3) in comparison to petrol station (73.08 ± 30.41 μg/m3), petrochemical industry (32.10 ± 13.13 μg/m3) and airport (25.30 ± 6.17 μg/m3). Strong correlations among BTEX compounds (p<0.01, r>0.7) at Kuala Lumpur City Centre showed that BTEX compounds originated from similar sources. The values of HQ at all stations were <1 indicating the non-carcinogenic risk are negligible and do not pose threats to human health. The LTCR value based on benzene inhalation (1.59 × 10-5) at Kuala Lumpur City Centre were between 1 × 10-4 and 1 × 10-5, representing a probable carcinogenic risk.
Benzene, toluene, ethylbenzene and xylenes (BTEX) are well known hazardous volatile organic compounds (VOCs) due to their human health risks and photochemical effects. The main objective of this study was to estimate BTEX levels and evaluate interspecies ratios and ozone formation potentials (OFP) in the ambient air of urban Kuala Lumpur (KL) based on a passive sampling method with a Tenax® GR adsorbent tube. Analysis of BTEX was performed using a thermal desorption (TD)-gas chromatography mass spectrometer (GCMS). OFP was calculated based on the Maximum Incremental Reactivity (MIR). Results from this study showed that the average total BTEX during the sampling period was 66.06 ± 2.39 μg/m3. Toluene (27.70 ± 0.97 μg/m3) was the highest, followed by m,p-xylene (13.87 ± 0.36 μg/m3), o-xylene (11.49 ± 0.39 μg/m3), ethylbenzene (8.46 ± 0.34 μg/m3) and benzene (3.86 ± 0.31 μg/m3). The ratio of toluene to benzene (T:B) is > 7, suggesting that VOCs in the Kuala Lumpur urban environment are influenced by vehicle emissions and other anthropogenic sources. The average of ozone formation potential (OFP) value from BTEX was 278.42 ± 74.64 μg/m3 with toluene and xylenes being the major contributors to OFP. This study also indicated that the average of benzene concentration in KL was slightly lower than the European Union (EU)-recommended health limit value for benzene of 5 μg/m3 annual exposure.
A thermal degradation pathway of the decolourisation of Reactive Cibacron Blue F3GA (RCB) in aqueous solution through catalytic thermolysis is established. Catalytic thermolysis is suitable for the removal of dyes from wastewater as it breaks down the complex dye molecules instead of only transferring them into another phase. RCB is a reactive dye that consists of three main groups, namely anthraquinone, benzene and triazine groups. Through catalytic thermolysis, the bonds that hold the three groups together were effectively broken and at the same time, the complex molecules degraded to form simple molecules of lower molecular weight. The degradation pathway and products were characterized and determined through UV-Vis, FT-IR and GCMS analysis. RCB dye molecule was successfully broken down into simpler molecules, namely, benzene derivatives, amines and triazine. The addition of copper sulphate, CuSO4, as a catalyst, hastens the thermal degradation of RCB by aiding in the breakdown of large, complex molecules. At pH 2 and catalyst mass loading of 5 g/L, an optimum colour removal of 66.14% was observed. The degradation rate of RCB is well explained by first order kinetics model.
Polyimide/SiO(2) composite films were prepared from tetraethoxysilane (TEOS) and poly(amic acid) (PAA) based on aromatic diamine (4-aminophenyl sulfone) (4-APS) and aromatic dianhydride (3,3,4,4-benzophenonetetracarboxylic dianhydride) (BTDA) via a sol-gel process in N-methyl-2-pyrrolidinone (NMP). The prepared polyimide/SiO(2) composite films were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and thermogravimetric analysis (TGA). The FTIR results confirmed the synthesis of polyimide (4-APS/BTDA) and the formation of SiO(2) particles in the polyimide matrix. Meanwhile, the SEM images showed that the SiO(2) particles were well dispersed in the polyimide matrix. Thermal stability and kinetic parameters of the degradation processes for the prepared polyimide/SiO(2) composite films were investigated using TGA in N(2) atmosphere. The activation energy of the solid-state process was calculated using Flynn-Wall-Ozawa's method without the knowledge of the reaction mechanism. The results indicated that thermal stability and the values of the calculated activation energies increased with the increase of the TEOS loading and the activation energy also varied with the percentage of weight loss for all compositions.
A new home-made diffusive bag-type passive sampler called Lanwatsu was developed for benzene, toluene, ethylbenzene and xylene monitoring in roadside air. The passive samplers were outdoor validated and deployed together with two commercial passive samplers, Ultra I SKC Inc. and Radiello, for daily roadside air monitoring in East Asian cities including HoChiMinh, Hanoi, Cantho, Danang, Vungtau, Hue (Vietnam), Kuala Lumpur (Malaysia), Kyoto, Osaka (Japan), Nanjing (China) and Singapore in 2011. High daily benzene concentrations of 87, 52, 32, 23, 13, 12 and 48 µg/m³ were observed in HoChiMinh, Hanoi, Cantho, Danang, Hue, Vung Tau (Vietnam), and Kuala Lumpur (Malaysia), respectively. Kyoto and Osaka (Japan) were clean with daily benzene concentrations below 2.3 μg/m³. The daily benzene concentrations in Nanjing (China) and Singapore were 5.6 and 6.9 μg/m³, respectively. The three passive samplers were equivalent. Passive sampling by the Lanwatsu passive sampler is acceptable for daily outdoor benzene monitoring.
This paper reports the result of sewage pollution monitoring conducted in South and Southeast Asia during 1998-2003 using linear alkylbenzenes (LABs) as molecular tracers of sewage contamination. Eighty-nine water samples collected from Malaysia, Vietnam, and Japan (Tokyo), and 161 surface sediment samples collected from Tokyo, Thailand, Malaysia, Philippines, Vietnam, Cambodia, Indonesia, and India were analyzed for alkylbenzenes. The concentration range of SigmaLABs in river water particles in Southeast Asia (<0.005-0.913 microg/L) was comparable to or higher than those found in Tokyo (<0.005-0.638 microg/L). I/E ratios (a ratio of internal to external isomers of LABs) in tropical Asian waters were close to the value of LABs in raw sewage ( approximately 1) and much lower than those in secondary effluents (3-5). This suggests that untreated or inadequately treated sewage is discharged into the water. SigmaLABs concentrations in sediments from South and Southeast Asia ranged from <0.002-42.6 microg/g-dry with the highest concentration occurring at several populous cities. Low I/E ratios of the sediments with high SigmaLABs concentrations suggest a heavy load of untreated sewage. Clearly in view of the current data and evidence of the implications of sewage pollution, this paper highlights the necessity of the continuation of water treatment system improvement in tropical Asia.
Even though drug-eluting stent (DES) has prominently reduced restenosis, however, its complication of delayed endothelialization has caused chronic side effect. A coating of ginseng-based biodegradable polymer could address this issue due to its specific therapeutic values. However, deposition of this type of stable coating on metallic implant often scarce. Therefore, in this study, different polyaniline (PANI) emeraldine compositions were adopted to electrodeposit ginsenoside encapsulated poly(lactic-co-glycolic acid) microcapsules coating. The coating surfaces were analyzed using attenuated total reflectance-Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, contact angle, and atomic force microscopy instruments. A month coating stability was then investigated with an evaluation of in vitro human umbilical vein endothelial cell analyses consisted of cytotoxicity and cells attachment assessments. The 1.5 mg PANI emeraldine has assisted the formation of stable, uniform, and rounded microcapsules coating with appropriate wettability and roughness. Less than 1.5 mg PANI emeraldine was not enough to drive the formation of microcapsules coating while greater than 1.5 mg caused the deposition of melted microcapsules. The similar coating also has promoted greater cells proliferation and attachment compared to other coating variation. Therefore, the utilization of electrodeposition to deposit a drug-based polymer coating could be implemented to develop DES, in accordance to stent implantation which ultimately aims for enrich endothelialization.
This is the first extensive report on linear alkylbenzenes (LABs) as sewage molecular markers in surface sediments collected from the Perlis, Kedah, Merbok, Prai, and Perak Rivers and Estuaries in the west of Peninsular Malaysia. Sediment samples were extracted, fractionated, and analyzed using gas chromatography mass spectrometry (GC-MS). The concentrations of total LABs ranged from 68 to 154 (Perlis River), 103 to 314 (Kedah River), 242 to 1062 (Merbok River), 1985 to 2910 (Prai River), and 217 to 329 ng g(-1) (Perak River) dry weight (dw). The highest levels of LABs were found at PI3 (Prai Estuary) due to the rapid industrialization and population growth in this region, while the lowest concentrations of LABs were found at PS1 (upstream of Perlis River). The LABs ratio of internal to external isomers (I/E) in this study ranged from 0.56 at KH1 (upstream of Kedah River) to 1.35 at MK3 (Merbok Estuary) indicating that the rivers receive raw sewage and primary treatment effluents in the study area. In general, the results of this paper highlighted the necessity of continuation of water treatment system improvement in Malaysia.
The impacts of rubber variations (clonal, seasonal, and pre-treatment) were investigated to assess changes in the composition of volatile organic compounds (VOCs) emitted during rubber processing. VOC emissions from 14 different rubber types were evaluated by headspace micro-chamber (μ-TEC) extraction coupled with gas chromatography-mass spectrometry (GC-MS). Headspace extracted at 120 °C, which is equivalent to the drying temperature during rubber processing, revealed a significant number of odorants in terms of concentrations as well as odorant type. Volatile fatty acids (VFAs) such as acetic, propanoic, butanoic, pentanoic and hexanoic acids, were frequently detected at concentrations greater than their odour detection thresholds. Other odorous compounds including trimethylamine, p-cresol, butanone, indole, and phenol, were also detected. Emissions collected at ambient conditions represent odorants released during material storage (or maturation) and were dominated by benzene derivatives followed by ketones, aldehydes, esters, and acids. Emission composition during storage appeared to be governed by specific rubber properties such as protein and rubber moisture content. Seasonal variations revealed greater impacts on the concentration of VOCs for all studied clones, compared to pre-treatment variations, suggesting that the VOCs composition was seasonally dependent and may represents the 'potential' emissions from rubber as they are processed. A combination of sensorial and analytical measurements were used to produce odour wheels which may be used as tool to identify key malodours in onsite rubber processing. The linking of odours and odorants can facilitate communication between receptors (the public) and plant operators inorder to minimise odour impact and develop effective abatement and on-site management practices.
Volatile organic compounds in honey are known for their considerable impact on the organoleptic properties of honey, such as aroma, flavor, taste, and texture. The type and composition of volatile organic compounds are influenced by entomological, geographical, and botanical origins; thus, these compounds have the potential to be chemical markers. Sixty-two volatile compounds were identified using gas chromatography-mass spectrometry from 30 Heterotrigona itama (H. itama) honey samples from 3 different geographical origins. Hydrocarbons and benzene derivatives were the dominant classes of volatile organic compounds in the samples. Both clustering and discriminant analyses demonstrated a clear separation between samples from distant origins (Kedah and Perak), and the volcano plot supported it. The reliability and predictability of the partial least squares-discriminant analysis model from the discriminant analysis were validated using cross-validation (R2 : 0.93; Q2 : 0.83; accuracy: 0.97) and the permutation test (p 1.0) and the Kruskal-Wallis test (p
The detection of phenolic compounds, i.e. resorcinol (RC) catechol (CC) and hydroquinone (HQ) are important due to their extremely hazardous impact and poor environmental degradation. In this work, a novel and sensitive composite of electrochemically reduced graphene oxide-poly(Procion Red MX-5B)/gold nanoparticles modified glassy carbon electrode (GCE/ERGO-poly(PR)/AuNPs) was assembled for voltammetric detection of benzenediol isomers (RC, CC, and HQ). The nanocomposite displayed high peak currents towards the oxidation of RC, HQ, and CC compared to non-modified GCE. The peak-to-peak separations were 0.44 and 0.10 V for RC-CC and CC-HQ, respectively. The limit of detections were 53, 53, and 79 nM for HQ, CC, and RC with sensitivities of 4.61, 4.38, and 0.56 μA/μM (S/N = 3), respectively. The nanocomposite displayed adequate reproducibility, besides good stability and acceptable recoveries for wastewater and cosmetic samples analyses.
In this study, an organic solvent tolerant bacterial strain was isolated. This strain was identified as Pseudomonas sp. strain S5, and was shown to degrade BTEX (Benzene, Toluene, Ethyl-Benzene, and Xylene). Strain S5 generates an organic solvent-tolerant lipase in the late logarithmic phase of growth. Maximum lipase production was exhibited when peptone was utilized as the sole nitrogen source. Addition of any of the selected carbon sources to the medium resulted in a significant reduction of enzyme production. Lower lipase generation was noted when an inorganic nitrogen source was used as the sole nitrogen source. This bacterium hydrolyzed all tested triglycerides and the highest levels of production were observed when olive oil was used as a natural triglyceride. Basal medium containing Tween 60 enhanced lipase production to the most significant degree. The absence of magnesium ions (Mg2+) in the basal medium was also shown to stimulate lipase production. Meanwhile, an alkaline earth metal ion, Na+, was found to stimulate the production of S5 lipase.