Three main types of PVC solvent polymeric membrane ion-selective electrodes for chloroquine are described. They are based on three ion-pairing agents namely dipicrylamine (DPA), tetraphenylborate (TPB) or tetrakis(4-chlorophenyl)borate (TCPB) with either dioctylphenyl phosphonate (DOPP) or trioctyl phosphate (TOP) solvent mediator. All electrodes exhibit Nernstian responses, fast dynamic response times and a wide useful pH range. The best all-round electrode is based on TPB and TOP plasticizing solvent mediators with a limit of detection of 7.1 x 10(-6)M and was utilized for the assay of chloroquine in tablets. Direct potentiometric determinations with either the analyte addition method or the normal calibration method gave results comparable to the official method.
A flow injection potentiometric method for the rapid determination of paraquat in herbicide formulations and biological samples is described. It is based on the utilization of a flow-through potentiometric detector containing polyvinyl chloride-immobilised octamethylcyclotetrasiloxane, a lipophilic plasticizer (tetra-n-undecyl 3,3',4,4'-benzophenone tetracarboxylate) and membrane additive potassium tetrakis(4-chlorophenyl)borate. The detector was minimally interfered by the presence of constituents such as Na(+), K(+), Ca(2+), Mg(2+), glucose, urea, lactic and citric acids at physiological levels, respectively. Good correlation between results of the proposed method and HPLC for the formulation samples was found, while results for the determination of paraquat in biological samples such as urine, vomitus and stomach washout was less satisfactory.
Poly (vinyl chloride) membrane electrodes that responded selectively towards the antimalarial drug chloroquine are described. The electrodes were based on the use of the lipophilic potassium tetrakis(4-chlorophenyl)borate as ion-exchanger and bis(2-ethylhexyl)adipate (BEHA), or trioctylphosphate (TOP) or dioctylphenylphosphonate (DOPP) as plasticizing solvent mediator. All electrodes produced good quality characteristics such as Nernstian- and rapid responses, and are minimally interfered with by the alkali and alkaline earth metal ions tested. The membranes were next applied to a flow-through device, enabling it to function as flow-injection analysis (FIA) detector. The performance of the sensor after undergoing the FIA optimization was further evaluated for its selectivity characteristics and lifetime. Results for the determination of chloroquine in synthetic samples that contained common tablet excipients such as glucose, starch, and cellulose, and other foreign species such as cations, citric acid or lactic acid were generally satisfactory. The sensor was also successfully used for the determination of the active ingredients in mock tablets, synthetic fluids and biological fluids. The sensor was applied for the determination of active ingredients and the dissolution profile of commercial tablets was also established.
Coating has been widely used in pharmaceutical manufacture either as non-functional or a functional entity. The objectives of the present study were to investigate the effect of plasticizers such as PEG400, PEG1000 and triacetin on mechanical properties, glass transition temperature and water vapor transmission of free films prepared from HPMC and/or HPMC:PVA blends, to develop suitable coating system for tablets, and to determine the release profiles of the coated tablets. The tensile strength of plasticized HPMC films was generally lower than that of control HPMC film and could be attributed to increased crystallinity and segmental chain mobility of HPMC. This effect increased as the concentration of plasticizer increased. Generally the addition of both grades of polyethylene glycol (PEG400 & PEG1000) increased the moisture permeability of HPMC films but the films containing triacetin provided a more rigid barrier to moisture compared to unplasticized HPMC films. The dissolution profiles of paracetamol tablets coated with 7% w/v HPMC coating-solutions containing PEG400, PEG1000 and triacetin, and those containing PEG400 & PVA together showed that HPMC had weak water resistance. The presence of PEG400 and 1000 in HPMC films further weakened its resistance to solubility while the presence of triacetin caused a little increase in HPMC water resistance. From the results it was concluded that HPMC at 7%w/w concentration was suitable for film-coating intended for non-functional coating. Presence of the PEG 400, PEG1000 and triacetin as well as the presence of PVA and PEG400 together improved the coating properties of HPMC films and made it more suitable as a non-functional coating material.
Fourier transform infrared (FT-IR) spectroscopic studies have been undertaken to investigate the interactions among components in a system of hexanoyl chitosan-lithium trifluoromethanesulfonate (LiCF(3)SO(3))-diethyl carbonate (DEC)/ethylene carbonate (EC). LiCF(3)SO(3) interacts with the hexanoyl chitosan to form a hexanoyl chitosan-salt complex that results in the shifting of the N(COR)(2), CONHR and OCOR bands to lower wavenumbers. Interactions between EC and DEC with LiCF(3)SO(3) has been noted and discussed. Evidence of interaction between EC and DEC has been obtained experimentally. Studies on polymer-plasticizer spectra suggested that there is no interaction between the polymer host and plasticizers. Competition between plasticizer and polymer on associating with Li(+) ions was observed from the spectral data for gel polymer electrolytes. The obtained spectroscopic data has been correlated with the conductivity performance of hexanoyl chitosan-based polymer electrolytes.
Chemical modification of natural rubber (NR) has frequently been attempted to improve the performance in specific application. 30% poly(methyl metacrylate) (PMMA) grafted into NR (MG30) has been explored as a potential candidate for polymer electrolytes. The complexation effect of salt and plasticizer in polymer host electrolytes had been investigated using FTIR. The carbonyl stretch of MG30 locates at 1729 cm-1, with the addition of lithium trimethanesulfonate (LiCF3SO3) salt, new band evolves at lower frequency region at 1643-1645 cm-1. The nondegenerate vibrational mode of nus(SO3) of salted electrolytes appearing at 1031-1034 cm-1 comes from 'free' trimethanesulfonate anions and the 1040-1046 cm-1 absorption from the monodentate ion paired with triflates. These indicate MG30-salt interaction. When MG30 and ethylene carbonate (EC) formed film, the CH3 asymmetric bend of MG30 appearing at 1447cm-1 is shifted to 1449 cm-1 in the EC-polymer complex. The CO stretching at 1729 cm-1 also shifted to 1728 cm-1. Hence, the EC-MG30 system is complexed to each other. EC-LiCF3SO3 interactions are indicated by the shifting of CO bending band of EC from 718 cm-1 being shifted to 720 cm-1 in the complex. In Li+-EC interaction where the ring breathing region at 897 cm-1 in EC has shifted to 899 cm-1 in EC-salt spectrum. The band appearing at 1643-1645 cm-1 due to the coordination of Li+
This paper describes the preparation of and experimentation undertaken by heterogeneous chitosan membrane as ion selective electrode for glutamate ion. The linearity response was obtained in the range of 1.0x10(-5) to 1.0x10(-1)M with a detection limit of 1.0x10(-6)M. The performance of the electrode was found in the pH range of 4.0-8.0 at temperature 25+/-3 degrees C. The response time was at 5-35s and was useful for a period of more than 4 months. The selectivity values towards some anions indicates good selectivity over a number of interfering anions. No significant improvement of membrane performance over additional of plasticizers such as 2-NPOE, BEHA and DOPP. The electrodes gave sufficient Nernstian responses with the exception of membrane with 2-NPOE.
The capacity of microwave non-destructive testing (NDT) technique to characterize the matrix property of binary polymeric films for use as transdermal drug delivery system was investigated. Hydroxypropylmethylcellulose (HPMC) and polyethylene glycol (PEG) 3000 were the choice of polymeric matrix and plasticizer, respectively with loratadine as the model drug. Both blank and drug loaded HPMC-PEG 3000 films were prepared using the solvent-evaporation method. These films were conditioned at the relative humidity of 25, 50 and 75% prior to physicochemical characterization using the established methods of ultra-violet spectrophotometry, differential scanning calorimetry and Fourier transform infrared spectroscopy methods, as well as, novel microwave NDT technique. Blank films exhibited a greater propensity of polymer-polymer interaction at the O-H domain upon storage at a lower level of relative humidity, whereas drug loaded films exhibited a greater propensity of polymer-polymer, polymer-plasticizer and/or drug-polymer interaction via the O-H, C-H and/or aromatic C=C functional groups when they were stored at a lower or moderate level of relative humidity. The absorption and transmission characteristics of both blank and drug loaded films for microwave varied with the state of polymer-polymer, polymer-plasticizer, and/or drug-polymer interaction of the matrix. The measurements of microwave NDT test at 8 and 12 GHz were sensitive to the polar fraction of film involving functional group such as O-H moiety and the less polar environment of matrix consisting of functional groups such as C-H and aromatic C=C moieties. The state of interaction between polymer, plasticizer and/or drug of a binary polymeric film can be elucidated through its absorption and transmission profiles of microwave.
Antibacterial effect of modified sago starch-alginate edible film incorporating lemongrass oil at various concentrations was studied. Edible films were prepared from a mixture of modified sago starch and alginate. Lemongrass oil (0.1 - 0.4%, v/w) and glycerol (0 and 20%, w/w) were incorporated in the films to act as natural antimicrobial agent and plasticizer, respectively. The films were characterized for antibacterial activity against food pathogenic bacteria such as Escherichia coli O157:H7, Salmonella Enteritidis and Staphylococcus aureus. The edible film exhibited antibacterial activity against Escherichia coli O157:H7 and Salmonella Enteritidis by using agar diffusion assay method. For films tested against Escherichia coli O157:H7, the zone of inhibition increased significantly (p < 0.05) with addition of lemongrass oil at all levels both in the presence and absence of glycerol. The films also significantly (p < 0.05) inhibited the growth of Salmonella enteritidis only with 0.4% lemongrass oil (in the presence and absence of glycerol). However, the films containing lemongrass oil did not show any inhibition effect on Staphylococcus aureus.
The objective of this research was to formulate an aerosol concentrate containing haruan (Channa
striatus) water extract that would produce a thin film when sprayed onto a wound and could be used for wound dressing. The aerosol concentrates were formulated with various polymer and plasticiser mixtures and tested in dispersion systems. The polymers evaluated were hydroxypropyl methylcellulose (HPMC), carboxymethylcellulose sodium (CMC Sodium), acacia, tragacanth, chitosan, gelatine and gelatine (bloom 151–160), all at concentrations of 2%. The plasticisers evaluated were polyethylene glycol (PEG) 400 and 4000, glycerine, propylene glycol, and triacetin. Films were prepared from film-forming dispersions by casting techniques. Film-forming dispersions were characterised in terms of pH, density, surface tension, rheological properties, particle size distribution, and tackiness. Based on these evaluations, HPMC was chosen as the best polymer. It produced a film with the expected qualities and was easy to reproduce in the form of dispersions or as thin transparent films. Glycerine was judged as the most appropriate plasticiser because it produced the concentrate having the desired qualities and properties expected from an aerosol concentrate.
Several blends of cellulose derived from bast part of kenaf (Hibiscus cannabinus L.) plant, with different thermoplastics, low density polyethylene (LDPE) and high density polyethylene (HDPE), were prepared by a melt blending machine. Polyethylene glycol (PEG) was used as plasticizer. Biodegradability of these blends was measured using soil burial test in order to study the rates of biodegradation of these polymer blends. It was found that the cellulose/LDPE and cellulose/HDPE blends were biodegradable in a considerable rate. The bio-composites with high content of cellulose had higher degradation rate. In addition, biodegradability of the bio-composites made up using PEG was superior to those of the bio-composites fabricated without PEG, due to the improved wetting of the plasticizer in the matrix polymer. The results were also supported by the scanning electron microscopy (SEM).
Linearity assessment as required in method validation has always been subject to different interpretations and definitions by various guidelines and protocols. However, there are very limited applicable implementation procedures that can be followed by a laboratory chemist in assessing linearity. Thus, this work proposes a simple method for linearity assessment in method validation by a regression analysis that covers experimental design, estimation of the parameters, outlier treatment, and evaluation of the assumptions according to the International Union of Pure and Applied Chemistry guidelines. The suitability of this procedure was demonstrated by its application to an in-house validation for the determination of plasticizers in plastic food packaging by GC.
The specific heats (Csp) of neat polyvinyl alcohol (NPVOH) and 40 phr glycerol plasticized polyvinyl alcohol (PPVOH) were measured using a method known as power compensate differential scanning calorimetry. A high purity sapphire (Al2O3) was used as a reference material. NPVOH has a melting temperature of approximately 480 K, while PPVOH has a value of 30 K lower than NPVOH. The amplitude increment of Csp for NPVOH was also higher than PPVOH at melting stage. Overall, Csp of NPVOH is lower than PPVOH because glycerol has reduced the rigidity of PVOH and subsequently induced the motion of molecular structure at an elevated temperature. Based on the specific heat outcomes, neat PVOH and glycerol plasticized PVOH required 1173.544 J/g and 1946.631 J/g, respectively, to heat from 330 to 550 K.
Polyethylene is a widely used packaging material, but its non-biodegradable nature can lead to waste
disposal problems. This increases the concern in research and development of biodegradable plastics from natural resource as alternatives to petroleum-derived plastics. In this study, biodegradable plastic composites were prepared by blending thermoplastic starch with natural rubber in the present of glycerol as plasticizer. Local sago starch was cast with 0.5 to 10% of natural rubber to prepare the bioplastic. The products were characterized by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), water absorption test, biodegradable test, hydrolysis test, and mechanical analysis. Meanwhile, composite with natural rubber latex was increased from 0.5 to 10% showing that the melting temperature is in the range of 120 to 150˚C, but with no significant difference. The water absorption characteristics, biodegradability, and tensile strength decreased by 11.21%, 30.18%, and 20.733 MPa, respectively. However, the elongation at break was increased from 26.67 to 503.3%. The findings of this study showed that sago starch has a great potential in bioplastic production with good miscibility and compatibility.
In this study polymer electrolytes composed of poly(methyl methacrylate) (PMMA) as a host polymer and ethylene carbonate (EC) as a plasticizer complexed with different lithium salts, i.e. lithium tetrafluoroborate (LiBF4) and lithium triflate (LiCF3SO3) were prepared by the solution casting technique. The conductivities of the films were characterized by impedance spectroscopy. At room temperature, the highest conductivities were 4.07 × 10–7S cm–1 and 3.40 × 10–5 S cm–1 achieved, respectively from the films containing 30 wt% LiBF4 in the PMMA-EC-LiBF4 system and 35 wt% LiCF3SO3 in the PMMA-EC-LiCF3SO3 system. The conductivity-temperature dependence of the films seemed to obey the Arrhenius equation in which the ion transport in these materials was thermally assisted. Scanning electron microscopy analysis showed that the surface of PMMA-EC-LiCF3SO3 film was smooth and homogeneous, hence lithium ions could traverse through the PMMA-EC-LiCF3SO3 film more easily compared to the PMMA-EC-LiBF4 film. X-Ray diffraction studies revealed that complexation had occurred and the complexes formed were amorphous.
Fourier transform infrared (FTIR) spectroscopy studies of poly(vinyl alcohol) (PVA), and chitosan polymer blend doped with ammonium nitrate (NH(4)NO(3)) salt and plasticized with ethylene carbonate (EC) have been performed with emphasis on the shift of the carboxamide, amine and hydroxyl bands. 1% acetic acid solution was used as the solvent. It is observed from the chitosan film spectrum that evidence of polymer-solvent interaction can be observed from the shifting of the carboxamide band at 1660 cm(-1) and the amine band at 1591 cm(-1) to 1650 and 1557 cm(-1) respectively and the shift of the hydroxyl band from 3377 to 3354 cm(-1). The hydroxyl band in the spectrum of PVA powder is observed at 3354 cm(-1) and is observed at 3343 cm(-1) in the spectrum of the PVA film. On addition of NH(4)NO(3) up to 30 wt.%, the carboxamide, amine and hydroxyl bands shifted from 1650, 1557 and 3354 cm(-1) to 1642, 1541 and 3348 cm(-1) indicating that the chitosan has complexed with the salt. In the PVA-NH(4)NO(3) spectrum, the hydroxyl band has shifted from 3343 to 3272 cm(-1) on addition of salt from 10 to 30 wt.%. EC acts as a plasticizing agent since there is no shift in the bands as observed in the spectrum of PVA-chitosan-EC films. The mechanism of ion migration is proposed for the plasticized and unplasticized PVA-chitosan-NH(4)NO(3) systems. In the spectrum of PVA-chitosan-NH(4)NO(3)-EC complex, the doublet CO stretching in EC is observed in the vicinity 1800 and 1700. This indicates that there is some interaction between the salt and EC.
The occurrence of 14 phthalate metabolites was found in human urine samples collected from seven Asian countries: China, India, Japan, Korea, Kuwait, Malaysia, and Vietnam. Phthalate metabolites were found in all samples, indicating widespread exposure of humans to phthalates in these Asian countries. The highest total (the sum of 14 phthalates) phthalate metabolite concentrations were found in samples collected from Kuwait (median: 1050 ng/mL), followed in decreasing order by samples from India (389 ng/mL), China (234 ng/mL), Vietnam (133 ng/mL), Japan (120 ng/mL), Korea (117 ng/mL), and Malaysia (94.9 ng/mL). The creatinine-adjusted median concentrations of total phthalates for urine samples from Kuwait, India, China, Vietnam, Japan, Korea, and Malaysia were 692, 506, 289, 119, 103, 104, and 169 μg/g creatinine, respectively. Monomethyl phthalate (mMP), monoethyl phthalate (mEP), mono (2-isobutyl phthalate) (miBP), mono-n-butyl phthalate (mBP), and metabolites of di-(2-ethylhexyl) phthalate (DEHP) were the dominant compounds, collectively accounting for >95% of the total concentrations in the samples from the seven countries. The profiles of urinary phthalate metabolite concentrations varied among the samples collected from the seven countries. Urine samples from Kuwait contained the highest concentrations of mEP (median: 391 ng/mL), mBP (94.1 ng/mL), and the metabolites of DEHP (202 ng/mL), whereas samples from China and Japan contained the highest concentrations of miBP (50.8 ng/mL) and mMP (17.5 ng/mL), respectively. mEP was the predominant metabolite in urine samples from India and Kuwait (accounting for 49% of the total), mBP and miBP were the predominant compounds in samples from China (52%), and DEHP metabolites were the predominant compounds in samples from Korea (46%) and Vietnam (52%). Based on the urinary concentrations of mEP, mBP, miBP, and DEHP metabolites of the samples from the seven Asian countries, we estimated daily intake rates of diethyl phthalate (DEP), dibutyl phthalate (DBP), and DEHP. The results indicated that people in the seven Asian countries are exposed to DEP, DBP, and DEHP at levels well below the reference doses (RfD) suggested as unsafe by the U.S. Environmental Protection Agency (EPA). The estimated exposure doses to DEHP in Kuwait, however, were above the RfD recommended by the EPA.
Polymer electrolytes based on polyacrylonitrile (PAN) containing inorganic salts; lithium triflate (LiCF3SO3) and sodium triflate (NaCF3SO3) and ethylene carbonate (EC) as plasticizer were prepared using solvent casting technique. In this study, five systems of plasticized and unplasticized polymer electrolyte films i.e. PAN-EC, PAN-LiCF3SO3, PAN-NaCF3SO3 PAN-EC-LiCF3SO3 and PAN-EC-NaCF3SO3 systems have been prepared. The structural and morphological properties of the films were studied using infrared spectroscopy and scanning electron microscopy (SEM) while the conductivity study was done by using impedance spectroscopy. The infrared results revealed that interaction had taken place between the nitrogen atoms of PAN and Li+ and Na+ ions from the salts. SEM micrographs showed that the plasticized film, PAN-EC-NaCF3SO3 has bigger pores than PAN-EC-LiCF3SO3 film resulting in the film containing NaCF3SO3 salt being more conductive. On addition of salts and plasticizer, the conductivity of pure PAN increases to three orders of magnitude. The plasticized film containing NaCF3SO3 salt has a higher conductivity compared to that containing LiCF3SO3 salt. This result showed that the interaction between Li+-ion and the nitrogen atom of PAN was stronger than that of Na+-ion. The conductivity-temperature dependence of the highest conducting film from each system follows Arrhenius equation in the temperature range of 303 to 353 K. The conductivity-pressure study in the range of 0.01 - 0.09 MPa showed that the conductivity decreased when pressure was increased. This can be explained in term of free volume model.
Several methods of incorporating sago pith waste (SPW) into poly(vinyl alcohol) (PVA) had been conducted: (i) dry blending (PVA/SPW/G), (ii) blending of SPW and pre-plasticized PVA (pPVA/SPW/G) and (iii) blending of pre-plasticized of both PVA and SPW (pPVA/pSPW). The effect of the compounding method on the mechanical and water absorption properties were investigated. The addition of SPW into PVA greatly reduced the tensile strength and elongation at break. The tensile strength and elongation at break of PVA/SPW composites with identical geometry during compounding stage (powder/powder and pellet/pellet), which were PVA/SPW/G and pPVA/pSPW yielded the highest value. The percentage of water absorbed by PVA/SPW/G (without pre-plasticization) was the highest, followed by pPVA/pSPW and pPVA/SPW/G.
Poly(lactic acid) (PLA) is known to be a useful material in substituting the conventional petroleum-based polymer used in packaging, due to its biodegradability and high mechanical strength. Despite the excellent properties of PLA, low flexibility has limited the application of this material. Thus, epoxidized palm olein (EPO) was incorporated into PLA at different loadings (1, 2, 3, 4 and 5 wt%) through the melt blending technique and the product was characterized. The addition of EPO resulted in a decrease in glass transition temperature and an increase of elongation-at-break, which indicates an increase in the PLA chain mobility. PLA/EPO blends also exhibited higher thermal stability than neat PLA. Further, the PLA/1 wt% EPO blend showed enhancement in the tensile, flexural and impact properties. This is due to improved interaction in the blend producing good compatible morphologies, which can be revealed by Scanning Electron Microscopy (SEM) analysis. Therefore, PLA can be efficiently plasticized by EPO and the feasibility of its use as flexible film for food packaging should be considered.