Solvent abuse is deliberate sniffing of an organic solvent for the intention of altering the physiological state of the individual. It is also commonly known as glue sniffing because glue is the most commonly abused substance. This form of substance abuse is widespread throughout the world and usually popular among secondary school children and young adults because of its easy availability and it is cheaper compared with most drugs of abuse. In Malaysia this problem has been recognized especially among the children in East Malaysia. In this study, 37 children and young adults from or around Kota Kinabalu, Sabah were referred to Bukit Padang Psychiatric Hospital by the Anti-drug Task force for suspected solvent abuse. These children were interviewed using questionaire and examined physically. Blood and urine were analysed for toluene and hippuric acid. 27 of the children, age ranging between 8 and 20 years, willingly admitted to sniffing glue for a period between a few months to 2 years. Most of them were children of Fillipino illegal immigrants in Kota Kinabalu. Biochemical parameters were found to be normal. Two of them were pale with low hemoglobin and 7 had eosinophilia. Haematuria and proteinuria were found in 21 children (78%). 16 blood samples with toluene levels ranging from 0.3 to 41 microg/ml and 10 urine samples have elevated urinary hippuric acid levels ranging from 1.2 to 7.4 mg/ml. Strong positive correlation was noted between mean blood toluene levels and duration of abuse.
The deliberate inhalation of solvents among children and adolescents "for kicks" is becoming more common in the West. It was generally regarded as a relatively harmless practice and consequently little attention had been paid to the isolation of the toxic agent from the variety of substances used. It is now well recognised that solvent abuse not only can result in sudden death but also cause pathological changes to the liver, kidney, brain, heart and lungs. A case of toluene associated death in Malaysia is discussed both from a medico-legal and pathological standpoint.
A new, rapid and sensitive microextraction technique named vortex-assisted liquid-liquid-liquid microextraction (VALLLME) is proposed. The complete extraction process involves two steps. First, a vortex-assisted liquid-liquid microextraction (VALLME) procedure was used to extract the analytes from a relatively large volume of sample (donor phase) to a small volume of organic solvent (intermediate phase). Next, a micro-vortex-assisted liquid-liquid extraction (µ-VALLE) was used to extract the target analytes from the intermediate phase to a smaller volume of aqueous solution (acceptor phase). The final extract (acceptor phase) can be directly injected into the high performance liquid chromatography or capillary electrophoresis units without any further treatments. The selection of the intermediate phase and the manipulation of pH are key parameters that ensure good extraction efficiency of the technique. The proposed technique has been successfully applied for the determination of carvedilol (used as model analyte) in biological fluid samples. The optimum extraction conditions were: toluene as intermediate phase (150 μL); pH of the donor phase, 9.5; vortex time of the VALLME, 45 s (maximum speed, 2500 rpm); 0.1M HCl (15 μL) as acceptor phase; vortexing time of the µ-VALLME, 75 s (maximum stirring speed, 2500 rpm) and salt concentration in the donor phase, 5% (w/v). Under these conditions, enrichment factors of 51- and 418-fold for VALLME step and VALLLME procedure, respectively, were achieved.
Surface modification of rice husk (RH) with alkali pre-treatment (NaOH solution 5% w/v) was carried out at the initial state to investigate the effect of surface treatment of fibre on the surface interaction between fibre and rubber. Further modification of RH surfaces after alkali treatment was using Liquid Epoxidized Natural Rubber (LENR) coating at three concentrations, 5%, 10%, and 20% wt LENR solution in toluene. Interfacial morphology and chemical reactions between RH fibre and rubber were analyzed by FTIR and Scanning Electron Microscope (SEM). It was found that 10% wt LENR solution gave the optimum interaction between fibre and rubber. Matrix and composite blends derived from 60% natural rubber (NR), 40% high density polyethylene (HDPE) reinforced with RH fibre were prepared using an internal mixer (Brabender Plasticoder). Result showed that pre-treatment of RH treated with 5% NaOH followed by treatment with 10% LENR solution given the maximum interaction between fibre and matrix that gave rise to better mechanical properties of the composites.
Toluene (C7H8) a hydrocarbon in crude oil, is a common contaminant in soil and groundwater. In this study, the ability to degrade toluene was investigated from twelve bacteria isolates which were isolated from soil contaminated with oil. Out of 12 bacterial isolates tested, most of Pseudomonas sp. showed the capability to grow in 1 mM of toluene compared with other isolates on the third day of incubation. Based on enzyme assays towards toluene monooxygenase, Pseudomonas aeruginosa UKMP-14T and Bacillus cereus UKMP-6G were shown to have the highest ability to degrade toluene. The toluene monoxygenase activity was analysed by using two calorimetric methods, Horseradish peroxidase (HRP) and indole-indigo. Both of the methods measured the production of catechol by the enzymatic reaction of toluene monooxygenase. In the HRP assay, the highest enzyme activity was 0.274 U/mL, exhibited by Pseudomonas aeruginosa UKMP-14T. However, for indole-indigo assay, Bacillus cereus UKMP-6G produced the highest enzyme activity of 0.291 U/ml. Results from both experiments showed that Pseudomonas aeruginosa UKMP-14T and Bacillus cereus UKMP-6G were able to degrade toluene.
Titanium dioxide (TiO2), porphyrin and TiO2 coated with dye porphyrin thin films were prepared on Quartz Crystal Microbalance (QCM) using sol-gel dip coating method and were tested for sensing of volatile organic compounds (VOCs). The porphyrin used was 5,10,15,20-tetraphenyl-21H,23H-porphine manganese (III) chloride (MnTPPCl). The sensing sensitivity was based on the change in the fundamental frequency of the QCM upon exposure towards six vapor samples, namely ethanol, acetone, cyclohexane, toluene, o-xylene and 2-propanol. It was found that all the thin films were sensitive towards all the vapors. However, the TiO2 coated MnTPPCl thin film exhibit the most sensitive and has good selectivity property.
hlorophyll a is known as the prevailing light absorbing pigment giving a strong absorption and fluorescence emission in visible region. Quenching reactions of the chlorophyll a fluorescence by Fe(acac)3 were precisely investigated in various organic solvents which are benzene toluene, ethanol, methanol, dmf, dmso and acetonitrile. Electron transfer performance of chlorophyll a by Fe(acac)3 was investigated from oxidative quenching reaction. Herein, the simplified Rehm-Weller relationship was used to calculate the free energy change of the photo-induced electron transfer reaction. Emission intensity decreased when the concentration of Fe(acac)3 quencher was increased. Non-linear Stern-Volmer plots are found to be affected by inner filter effect more than the ground state complex formation. Rate of quenching reactions (kq) were determined from the Stern-Volmer equation with corrected inner filter effect. The rates of quenching reactions occurred faster in high viscous solvents.
In this work, we reported the synthesis, characterization and adsorption study of two β-cyclodextrin (βCD) cross-linked polymers using aromatic linker 2,4-toluene diisocyanate (2,4-TDI) and aliphatic linker 1,6-hexamethylene diisocyanate (1,6-HDI) to form insoluble βCD-TDI and βCD-HDI. The adsorption of 2,4-dinitrophenol (DNP) on both polymers as an adsorbent was studied in batch adsorption experiments. Both polymers were well characterized using various tools that include Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller analysis and scanning electron microscopy, and the results obtained were compared with the native βCD. The adsorption isotherm of 2,4-DNP onto polymers was studied. It showed that the Freundlich isotherm is a better fit for βCD-TDI, while the Langmuir isotherm is a better fit for βCD-HMDI. The pseudo-second-order kinetic model represented the adsorption process for both of the polymers. The thermodynamic study showed that βCD-TDI polymer was more favourable towards 2,4-DNP when compared with βCD-HDI polymer. Under optimized conditions, both βCD polymers were successfully applied on various environmental water samples for the removal of 2,4-DNP. βCD-TDI polymer showed enhanced sorption capacity and higher removal efficiency (greater than 80%) than βCD-HDI (greater than 70%) towards 2,4-DNP. The mechanism involved was discussed, and the effects of cross-linkers on βCD open up new perspectives for the removal of toxic contaminants from a body of water.
Toluene diisocyanate (TDI) is a major cause of chemical-induced occupational asthma, which contributes about 15% of global asthma burden. Resistance and compounded side effects associated with the use of corticosteroid in asthma necessitate the search for alternative drugs. Andrographolide (AGP), a naturally occurring diterpene lactone is known to exhibit various bioactivities. Its ability to ameliorate cardinal features of allergic asthma was previously suggested in an eosinophilic asthma endotype. However, its potential antiasthma activity and mechanism of action in a neutrophilic occupational asthma model, as well as its effect on epithelial dysfunction remain unknown. BALB/c mice were dermally sensitised with 0.3% TDI or acetone olive oil (AOO) vehicle on day 1 and 8, followed by 0.1% TDI intranasal challenge on days 15, 18 and 21. Endpoints were evaluated via bronchoalveolar lavage fluid (BALF) cell analysis, 2',7'-dichlorofluorescein diacetate (DCFDA) assays, immunoblotting, immunohistochemistry and methacholine challenge test. Decreases in total and differential leukocyte counts of BALF were recorded in AGP-treated animals. The compound dose-dependently reduced intracellular de-esterification of DCFDA, thus suggesting AGP's potential to inhibit intracellular reactive oxygen species (ROS). Mechanistically, the treatment prevented TDI-induced aberrant E-cadherin distribution and restored airway epithelial β-catenin at cell to cell contact site. Furthermore, AGP ameliorated TDI induced pulmonary collagen deposition. In addition, the treatment significantly upregulated pulmonary HO-1, Nrf2 and phospho-p38 levels. Airway hyperresponsiveness was markedly suppressed among AGP-treated animals. Collectively, these findings suggest AGP's protective function against TDI-induced airway epithelial barrier dysfunction and oxidative lung damage possibly through the upregulation of adherence junction proteins and the activation of p38/Nrf2 signalling. This study elucidates the therapeutic potential of AGP in the control and management of chemical-induced allergic asthma. To the best of our knowledge, the potential anti-asthma activity of AGP in TDI-induced occupational asthma has not been reported previously.
A 33-year-old man with a history of chronic toluene abuse through glue sniffing, developed tremors, cerebellar signs and cognitive decline. MR scan of the brain showed global cerebral and cerebellar atrophy with symmetrical T2-weighted hypointensities in the basal ganglia, thalami and midbrain. After stopping glue sniffing, his tremors, ataxia of gait, speech and cognition partially improved. Early recognition and intervention of toluene-induced leukodystrophy could prevent ongoing morbidity and premature mortality.
Palm fatty acid distillate (PFAD), is a by-product of the crude palm oil refining process. It comprises mainly of free fatty acids-around 45% palmitic and 33% oleic acids-as the major components. Ultra-violet (UV) curable urethane acrylate (UA) oligomers could be synthesized from PFAD, by the following procedure. A hydroxyl terminated macromer was first prepared by reacting PFAD with a mixture of isophthalic acid, phthalic anhydride, neopentagylcol (NPG), and pentaerythritol. The macromer was then reacted with 2-hydroxylethylacrylate (2HEA) and toluene diisocynate (TDI) to generate a resin, containing acrylate side chains for UV curable application. A series of UA resins were prepared by using 15, 25, 45, 55, and 70% of PFAD, respectively. The UA resin has Mw in the range of 3,200 to 27,000. They could be cured by UV irradiation at an intensity of 225 mW/cm². Glass transition temperature (Tg) of the cured film was measured by differential scanning calorimeter (DSC), and hardness of the film was determined by a pendulum hardness tester, according to American Society for Testing and Materials (ASTM)4366. The resins were used in a wood-coating application. All of the cured films showed good adhesion, hardness, and chemical resistance except for the one using the 70% PFAD, which did not cure properly.
Crude jatropha oil (JO) was modified to form jatropha oil-based polyol (JOL) via two steps in a chemical reaction known as epoxidation and hydroxylation. JOL was then reacted with isocyanates to produce JO-based polyurethane resin. In this study, two types of isocyanates, 2,4-toluene diisocyanate (2,4-TDI) and isophorone diisocyanate (IPDI) were introduced to produce JPUA-TDI and JPUA-IPDI respectively. 2,4-TDI is categorised as an aromatic isocyanate whilst IPDI is known as a cycloaliphatic isocyanate. Both JPUA-TDI and JPUA-IPDI were then end-capped by the acrylate functional group of 2-hydroxyethyl methacrylate (HEMA). The effects of that isocyanate structure were investigated for their physico, chemical and thermal properties. The changes of the functional groups during each synthesis step were monitored by FTIR analysis. The appearance of urethane peaks was observed at 1532 cm-1, 1718 cm-1 and 3369 cm-1 while acrylate peaks were detected at 815 cm-1 and 1663 cm-1 indicating that JPUA was successfully synthesised. It was found that the molar mass of JPUA-TDI was doubled compared to JPUA-IPDI. Each resin showed a similar degradation pattern analysed by thermal gravimetric analysis (TGA). For the mechanical properties, the JPUA-IPDI-based coating formulation exhibited a higher hardness value but poor adhesion compared to the JPUA-TDI-based coating formulation. Both types of jatropha-based polyurethane acrylate may potentially be used in an ultraviolet (UV) curing system specifically for clear coat surface applications to replace dependency on petroleum-based chemicals.
This study is an attempt to investigate the adsorption of petroleum hydrocarbon (toluene) from aqueous solutions using granular activated carbon (GAC) synthesized from oil palm shell (OPS) (referred as OPSbased GAC). This study involved a series of batch experiments to determine the adsorption equilibrium and kinetics. The batch experiments were conducted by shaking 200 mL toluene solution containing 0.4 g GAC (initial concentrations of 5, 15, 25 and 30 mg/L) at 180 rpm at 30°C. The OPS-based GAC achieved more than 80% toluene removal in all the experiments. The adsorption capacity of the OPSbased GAC estimated using Freundlich isotherm was 6.039 mg/g (L/mg)1/n. The adsorption kinetic study showed that the adsorption of toluene was of chemisorption as the experimental data fitted better to the pseudo-second-order kinetic model than the pseudo-first-order kinetic model.
The alkaline cold-active lipase from Pseudomonas fluorescens AMS8 undergoes major structural changes when reacted with hydrophobic organic solvents. In toluene, the AMS8 lipase catalytic region is exposed by the moving hydrophobic lid 2 (Glu-148 to Gly-167). Solvent-accessible surface area analysis revealed that Leu-208, which is located next to the nucleophilic Ser-207 has a focal function in influencing substrate accessibility and flexibility of the catalytic pocket. Based on molecular dynamic simulations, it was found that Leu-208 strongly facilitates the lid 2 opening via its side-chain. The KM and Kcat/KM of L208A mutant were substrate dependent as it preferred a smaller-chain ester (pNP-caprylate) as compared to medium (pNP-laurate) or long-chain (pNP-palmitate) esters. In esterification of ethyl hexanoate, L208A promotes a higher ester conversion rate at 20 °C but not at 30 °C, as a 27% decline was observed. Interestingly, the wild-type (WT) lipase's conversion rate was found to increase with a higher temperature. WT lipase AMS8 esterification was higher in toluene as compared to L208A. Hence, the results showed that Leu-208 of AMS8 lipase plays an important role in steering a broad range of substrates into its active site region by regulating the flexibility of this region. Leu-208 is therefore predicted to be crucial for its role in interfacial activation and catalysis in toluene.
Lactobacilli are well-documented probiotics that exert health benefits on their host. They exhibit characteristics that make them potential alternative treatments to address the antimicrobial resistance conundrum and diseases. Their mechanism of action varies with strain and species. Five lactobacilli strains previously isolated from the anogenital region were subjected to several assessments highlighted in the FAO/WHO document, ‘Guidelines for the Evaluation of Probiotics in Food’ to determine its suitability as potential probiotics. Methods: The five lactobacilli strains were subcultured onto Man de Rogosa agar (MRS). Their ability to auto- and co-aggregate was determined spectrophotometrically. Simultaneously, the cell surface hydrophobic properties of these strains towards xylene and toluene were evaluated using the microbial adhesion to hydrocarbon (MATH) test. The lactobacilli strains were also tested for their ability to withstand acid, bile and spermicide to determine their level of tolerance. Results: Lact. reuteri 29A, L. delbrueckii 45E and L. reuteri 29B exhibited the highest degree of auto- and co-aggregation properties. These lactobacilli strains also demonstrated high cell surface hydrophobicity, with the exception of L. delbrueckii 45E. Further tests to evaluate the isolated lactobacilli tolerance identified L. reuteri 29B as the most tolerant strain towards low pH (pH 2.5 for 4 h), high bile concentration (0.5% for 4 h) and high spermicides concentration (up to 10%). Conclusion: Out of the five lactobacilli strains which possessed high antimicrobial activities, L. reuteri 29B portrayed the best probiotic qualities with good auto- and co-aggregation abilities and high tolerance against acid, bile and spermicide.
The utilization of cold active lipases in organic solvents proves an excellent approach for chiral synthesis and modification of fats and oil due to the inherent flexibility of lipases under low water conditions. In order to verify whether this lipase can function as a valuable synthetic catalyst, the mechanism concerning activation of the lid and interacting solvent residues in the presence of organic solvent must be well understood. A new alkaline cold-adapted lipase, AMS8, from Pseudomonas fluorescens was studied for its structural adaptation and flexibility prior to its exposure to non-polar, polar aprotic and protic solvents. Solvents such as ethanol, toluene, DMSO and 2-propanol showed to have good interactions with active sites. Asparagine (Asn) and tyrosine (Tyr) were key residues attracted to solvents because they could form hydrogen bonds. Unlike in other solvents, Phe-18, Tyr-236 and Tyr-318 were predicted to have aromatic-aromatic side-chain interactions with toluene. Non-polar solvent also was found to possess highest energy binding compared to polar solvents. Due to this circumstance, the interaction of toluene and AMS8 lipase was primarily based on hydrophobicity and molecular recognition. The molecular dynamic simulation showed that lid 2 (residues 148-167) was very flexible in toluene and Ca(2+). As a result, lid 2 moves away from the catalytic areas, leaving an opening for better substrate accessibility which promotes protein activation. Only a single lid (lid 2) showed the movement following interactions with toluene, although AMS8 lipase displayed double lids. The secondary conformation of AMS8 lipase that was affected by toluene observed a reduction of helical strands and increased coil structure. Overall, this work shows that cold active lipase, AMS8 exhibits distinguish interfacial activation and stability in the presence of polar and non-polar solvents.
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.
The yeast strain Candida tropicalis was used for the biodegradation of gaseous toluene. Toluene was effectively treated by a liquid culture of C. tropicalis in a bubble-column bioreactor, and the toluene removal efficiency increased with decreasing gas flow rate. However, toluene mass transfer from the gas-to-liquid phase was a major limitation for the uptake of toluene by C. tropicalis. The toluene removal efficiency was enhanced when granular activated carbon (GAC) was added as a fluidized material. The GAC fluidized bioreactor demonstrated toluene removal efficiencies ranging from 50 to 82% when the inlet toluene loading was varied between 13.1 and 26.9 g/m(3)/h. The yield value of C. tropicalis ranged from 0.11 to 0.21 g-biomass/g-toluene, which was substantially lower than yield values for bacteria reported in the literature. The maximum elimination capacity determined in the GAC fluidized bioreactor was 172 g/m(3)/h at a toluene loading of 291 g/m(3)/h. Transient loading experiments revealed that approximately 50% of the toluene introduced was initially adsorbed onto the GAC during an increased loading period, and then slowly desorbed and became available to the yeast culture. Hence, the fluidized GAC mediated in improving the gas-to-liquid mass transfer of toluene, resulting in a high toluene removal capacity. Consequently, the GAC bubble-column bioreactor using the culture of C. tropicalis can be successfully applied for the removal of gaseous toluene.
Atmospheric pollution and global warming issues are increasingly becoming major environmental concerns. Fire is one of the significant sources of pollutant gases released into the atmosphere; and tropical biomass fires, which are of particular interest in this study, contribute greatly to the global budget of CO and CO2. This pioneer research simulates the natural biomass burning strategy in Malaysia using an experimental burning facility. The investigation was conducted on the emissions (CO2, CO, and Benzene, Toluene, Ethylbenzene, Xylenes (BTEX)) from ten tropical biomass species. The selected species represent the major tropical forests that are frequently subjected to dry forest fire incidents. An experimental burning facility equipped with an on-line gas analyzer was employed to determine the burning emissions. The major emission factors were found to vary among the species, and the specific results were as follows. The moisture content of a particular biomass greatly influenced its emission pattern. The smoke analysis results revealed the existence of BTEX, which were sampled from a combustion chamber by enrichment traps aided with a universal gas sampler. The BTEX were determined by organic solvent extraction followed by GC/MS quantification, the results of which suggested that the biomass burning emission factor contributed significant amounts of benzene, toluene, and m,p-xylene. The modified combustion efficiency (MCE) changed in response to changes in the sample moisture content. Therefore, this study concluded that the emission of some pollutants mainly depends on the burning phase and sample moisture content of the biomass.