This study focused on the development and optimization of a hybrid material formed from sol-gel and chitosan which could be used as a chemical sensing material. It is hoped that this new matrix can overcome certain weaknesses in solÂgel and chitosan materials. Dip-coating technique was used to prepare the film on microscope glass slide which functioned as a solid support. For optimization purposes, thymol blue was chosen as a pH indicator and was entrapped in the film. The film was characterized using uv-Visible Spectrophotometer. Morphology studies of the surface of the film were carried out using Scanning Electron Microscope (SEM). Results indicated that the most suitable solgel: chitosan ratio for hybrid formation was 60:40 after considering the surface morphology of the film, leaching, response time and also the intensities of the spectrum. Besides that, the results also show that the pH indicator could be successfully entrapped inside the hybrid film and would still retain its chemical behavior just as in solution. The sensing material was found to have good repeatability when reacted with buffer solution and showed RSD values of 4.24 % and 5.96 % in buffer solution at pH 2.0 and pH 11.0, respectively. The entrapped indicator also showed good photo stability with RSD of 5.35 % for the duration of 8 hours. However; the reproducibility of the hybrid film was quite low with a RSD value of 18.40 % and 31.22 % at wavelength of 500 nm and 600 nm, respectively due to leaching.
[Penyelidikan ini difokuskan kepada pembangunan dan pengoptimuman bahan hibrid antara sol-gel dan kitosan untuk membentuk suatu matriks baru bagi penyediaan bahan penderia kimia yang dapat mengatasi kekurangan tertentu dalam bahan sol-gel danjuga kitosan. Teknik penyalutan celup telah digunakan untuk penyediaan filem nipis di atas penyokong slaid kaca mikroskop. Untuk tujuan pengoptimuman, timol biru dipilih sebagai penunjuk pH dan dipegunkan di dalam filem. Filem nipis dicirikan menggunakan Spektrofotometer UL-Nampak. Kajian morfologi ke atas permukaan filem pula dilakukan dengan menggunakan Mikroskop Imbasan Elektron (MIE). Keputusan yang diperolehi menunjukkan bahawa nisbah sol-gel:kitosan yang paling sesuai ialah 60:40 dengan mempertimbangkan dari segi morfologi permukaan filem, kelarutresapan, masa rangsangan dan juga keamatan spektrum. Selain itu, keputusan menunjukkan bahawa penunjuk pH berjaya dipegunkan dalam filem hibrid sol-gel-kitosan dan mampu mengekalkan sifat kimianya sebagaimana dalam larutan. Bahan penderia kimia ini didapati mempunyai kebolehulangan yang baik apabila bertindak dengan larutan penimbal dan menunjukkan nilai RSD yang baik iaitu 4.24% dan 5.96% dalam larutan penimbal pH 2.0 dan pH 11.0, masing-masingnya. Penunjuk pH terpegun turut menunjukkan kestabilan foto yang baik (RSD = 5.35%) untuk tempoh 8 jam. Walau bagaimanapun, kebolehasilan filem agak rendah dengan RSD yang bernilai 18.40% dan 31.22 % pada panjang gelombang 550 nm dan 600 nm masing-masing akibat daripada kelarut resapan].
Artificial neural network (ANN) was used in this study to determine water turbidity by using back propagation algorithm. Three wavelengths which represent reflectance intensity for eight standard samples were used as training input. The finding from the study shows that the trained network with number of epochs of 250,000 and learning rate of 0.001 gave the lowest sum of squared error (SSE) of 0.04. ANN was able to predict the turbidity of water based on the pattern recognition of the reflectance spectrum. The architecture of optimized ANN used in this study was 3:25:1. The average prediction error was 0.02.
[Jaringan neural tiruan (ANN) dengan lagoritma perambatan balik (BP) telah digunakan dalam kajian ini untuk menentukan kekeruhan air. Tiga panjang gelombang yang mewakili serapan bagi lapan sampel telah dipilih sebagai imput latihan. Hasil kajian menunjukkan bagi jaringan terlatih dengan bilangan ulangan latihan 250,000 dan kadar pembelajaran 0.001 telah memberikan nilai SSE yang terendah iaitu 0.04. Dalam kajian ini jaringan ANN didapati boleh menentu dan meramalkan nilai kekeruhan sample air berdasarkan corak serapan pantulan. Arkitektur yang sesuai bagi kajian ini adalah 3:25:1. Purata ralat ramalan adalah 0.02].
Analisis kuantitatif untuk penentuan kepekatan ion Al3+ dalam larutan akueus telah dilakukan menggunakan reagen alizarin red S (ARS) melalui pembentukan kompleks ARS-Al(III) yang dianalisis menggunakan kaedah spektrofotometri UL-Nampak. Kompleks ARS-Al(III) memberikan puncak serapan pada panjang gelombang 484 nm pada pH 5. Kajian kestabilan foto bagi reagen ARS memberikan nilai RSD sebanyak 0.46 %. Analisis kebolehulangan memberikan nilai RSD sebanyak 1.07 % dan 0.67 % masing-masingnya bagi kepekatan Al(III) 0.2 ppm dan 9 ppm. Gangguan kation Cu2+ dan Fe3+ pada nisbah mol 1:10 adalah minimum. Kebanyakan anion penggangu tidak memberikan kesan gangguan kecuali F- pada nisbah mol 1:1 dan 1:10. Sistem ini memberikan julat kepekatan dinamik Al3+ antara 0.1 – 1.0 ppm. Arkitektur ANN dengan bilangan neuron terlindung, bilangan kitaran dan kadar pembelajaran adalah masing-masingnya 23, 40000 dan 0.001 telah berjaya memanjangkan julat dinamik kepekatan Al(III) daripada 0.1 – 8.0 ppm. Reagen ARS berjaya dipegunkan pada permukaan ko-polimer XAD 4 dan mampu memberikan respon optik yang baik terhadap ion Al3+.
Potensi larutan reagen fenilfluoron untuk digunakan sebagai bahan reagen bagi pembangunan sensor optik pH dibincangkan dalam kajian ini. Reagen ini dipilih kerana ia belum pernah dilaporkan sebelum ini untuk digunakan sebagai bahan reagen bagi pembangunan sensor optik pH. Berdasarkan kajian larutan yang telah dijalankan, julat rangsangan linear pH bagi reagen fenilfluoron ialah antara pH 4–11. Perubahan warna dapat diperhatikan, iaitu warna kuning dalam asid kuat, warna oren dalam asid lemah serta bes lemah dan warna ungu dalam bes kuat. Perubahan warna yang berlaku adalah lebih kurang 5 saat. Reagen fenilfluoron mempunyai kestabilan foto yang baik dengan nilai RSD 0.33% untuk tempoh kajian selama 95 hari. Nilai RSD bagi kebolehulangan pada pH 2, pH 7 dan pH 12 adalah masing-masingnya sebanyak 2.6%, 0.9% dan 1.4%. Pemerhatian ini menunjukkan fenilfluoron mempunyai potensi yang baik untuk digunakan sebagai bahan reagen bagi pembangunan sensor optik pH.
A quantitative analysis has been conducted to determine the concentration of ammonium (NH4+) ion in solution by using Ultraviolet-visible spectrophotometry method and artificial neural network (ANN). Riegler’s reagent was used to form Riegler-NH4+ complex. The characterisations of Riegler’s reagent in solution such as photostability, pH effect, reagent concentration, dynamic range and reproducibility were conducted. The colour change of the Riegler’s reagent after reaction with NH4+ was yellow to red. The Riegler’s reagent responds linearly to NH4+ ion concentration in the range of 1-7 ppm with optimum response at pH7. Satisfactory reproducibility (2.0-2.8%) were obtained with this reagent. The effect of interfering ions that may contain in the leachate on the determination of NH4+ ion was also studied. The application of ANN enabled the extension of the useful dynamic concentration range of NH4+ ion to 1–24 ppm. The best ANN architecture for Riegler-NH4+ complex was built from 29 hidden neurons, 21,389 epochs number and 0.001% learning rate which produced sum square error (SSE) value of 0.0483 with an average calibration error of 1.4136.
Kajian pemegunan enzim peroksidase dalam membran hibrid sol-gel-kitosan untuk penyediaan transduser optik hidrogen peroksida telah dilakukan dalam pembinaan biosensor. Kajian ini merangkumi pengoptimuman nisbah sol-gel-kitosan, pencirian enzim dalam larutan bebas dan pemegunan enzim dalam hibrid sol-gel-kitosan serta penciriannya. Spektrum serapan bagi setiap pencirian ditentukan menggunakan Spektrofotometer uL-Nampak. Hasil kajian menunjukkan aktiviti enzim tidak berubah selepas pemegunan. Nisbah optimum hibrid sol-gel-kitosan adalah 4:6. Nilai sisihan piawai relatif (RSD) untuk kebolehulangan kaedah ini adalah 2.71% dan 3.76%, masing-masingnya untuk enzim bebas dan enzim terpegun.
Molecularly imprinted polymer (MIP) based on acrylate monomer was prepared at 80°C for 5 hours using p-xylene and ethylene glycol dimethacrylate (EGDMA) as a template and crosslinking agent respectively. The polymer obtained was washed with a mixture of acetic acid and methanol (1:4) and dried in the vacuum oven at 80°C. FTIR spectrum showed that all the templates were leached out from polymer during excessive washing and drying stage. The rebinding test result showed that the MIP was bonded with the analyte in the presence of organic solvents as shown by FTIR spectroscopy. The SEM micrograph showed that non-imprinted polymer (NIP) had no cavity as compared to MIP.
In this work, a new optical screening method for acrylamide was developed. Bacterial Bacillus sp. strain ZK 34 was used to
hydrolyse acrylamide to the corresponding acid and ammonia. Nessler’s reagent was used to detect the produced ammonia
and the yellow complex formed was treated as signal. Bacterial pellet was immobilised in the alginate membrane. The
optimum composition of alginate used is 2%. The mass ratio of alginate:bacterial of 1:0.5 gave the optimum respond.
Optimum concentration for NaOH and Nessler’s reagent were 0.075 M and 2.5 mM, respectively. The yellow complex
of mercury (II) amido-iodine formed was directly proportional to the concentrations of acrylamide up to 50.00 ppm
with the limit of detection of 1.30 ppm. This sensor shows a good reproducibility which the relatives standard deviation
(RSD) values from 3.17-6.15%. Therefore, the detection of acrylamide based on the amidase hydrolysis is suitable for
screening this carcinogen compound.
An optical fiber chemical sensor for the determination of free glutamate in food samples was fabricated based on the
immobilization of 0.1 M copper(II) nitrate trihydrate onto sol-gel glass powder which was then mixed with methyl cellulose
to form a pellet. A distinctive colour change from light blue to dark blue was observed in the presence of glutamate in
less than 1 min. The colour change was measured by reflectance spectrophotometer at 691 nm. A linear relationship
between the reflectance intensity and glutamate concentration was observed in the range of 12.5 to 500 mM with a limit
of detection of 10.6 mM. This method is also reproducible with a relative standard deviation of less than 5%, no effect on
pH of the glutamate solution and a good recovery of above 80%. The sensor was used for the determination of glutamate
in common food items such as soups and flavor enhancers. The results obtained from the fabricated sensor were found
to be comparable with HPLC method.
The use of the enzyme alanine dehydrogenase (AlaDH) for the determination of ammonium ion (NH(4)(+)) usually requires the addition of pyruvate substrate and reduced nicotinamide adenine dinucleotide (NADH) simultaneously to effect the reaction. This addition of reagents is inconvenient when an enzyme biosensor based on AlaDH is used. To resolve the problem, a novel reagentless amperometric biosensor using a stacked methacrylic membrane system coated onto a screen-printed carbon paste electrode (SPE) for NH(4)(+) ion determination is described. A mixture of pyruvate and NADH was immobilized in low molecular weight poly(2-hydroxyethyl methacrylate) (pHEMA) membrane, which was then deposited over a photocured pHEMA membrane (photoHEMA) containing alanine dehydrogenase (AlaDH) enzyme. Due to the enzymatic reaction of AlaDH and the pyruvate substrate, NH(4)(+) was consumed in the process and thus the signal from the electrocatalytic oxidation of NADH at an applied potential of +0.55 V was proportional to the NH(4)(+) ion concentration under optimal conditions. The stacked methacrylate membranes responded rapidly and linearly to changes in NH(4)(+) ion concentrations between 10-100 mM, with a detection limit of 0.18 mM NH(4)(+) ion. The reproducibility of the amperometrical NH(4)(+) biosensor yielded low relative standard deviations between 1.4-4.9%. The stacked membrane biosensor has been successfully applied to the determination of NH(4)(+) ion in spiked river water samples without pretreatment. A good correlation was found between the analytical results for NH(4)(+) obtained from the biosensor and the Nessler spectrophotometric method.
The role of incorporation of gold nanoparticles (50-130 nm in diameter) into a series of photocurable methacrylic-acrylic based biosensor membranes containing tyrosinase on the response for phenol detection was investigated. Membranes with different hydrophilicities were prepared from 2-hydroxyethyl methacrylate and n-butyl acrylate via direct photocuring. A range of gold nanoparticles concentrations from 0.01 to 0.5 % (w/w) was incorporated into these membranes during the photocuring process. The addition of gold nanoparticles to the biosensor membrane led to improvement in the response time by a reduction of approximately 5 folds to give response times of 5-10 s. The linear response range of the phenol biosensor was also extended from 24 to 90 mM of phenol. The hydrophilicities of the membrane matrices demonstrated strong influence on the biosensor response and appeared to control the effect of the gold nanoparticles. For less hydrophilic methacrylic-acrylic membranes, the addition of gold nanoparticles led to a poorer sensitivity and detection limit of the biosensor towards phenol. Therefore, for the application of gold nanoparticles in the enhancement of a phenol biosensor response, the nanoparticles should be immobilized in a hydrophilic matrix rather than a hydrophobic material.
Magnetic nanoparticles of Fe₃O₄ were synthesized and characterized using transmission electron microscopy and X-ray diffraction. The Fe₃O₄ nanoparticles were found to have an average diameter of 5.48 ±1.37 nm. An electrochemical biosensor based on immobilized alkaline phosphatase (ALP) and Fe₃O₄ nanoparticles was studied. The amperometric biosensor was based on the reaction of ALP with the substrate ascorbic acid 2-phosphate (AA2P). The incorporation of the Fe₃O₄ nanoparticles together with ALP into a sol gel/chitosan biosensor membrane has led to the enhancement of the biosensor response, with an improved linear response range to the substrate AA2P (5-120 μM) and increased sensitivity. Using the inhibition property of the ALP, the biosensor was applied to the determination of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). The use of Fe₃O₄ nanoparticles gives a two-fold improvement in the sensitivity towards 2,4-D, with a linear response range of 0.5-30 μgL-1. Exposure of the biosensor to other toxicants such as heavy metals demonstrated only slight interference from metals such as Hg2+, Cu2+, Ag2+ and Pb2+. The biosensor was shown to be useful for the determination of the herbicide 2, 4-D because good recovery of 95-100 percent was obtained, even though the analysis was performed in water samples with a complex matrix. Furthermore, the results from the analysis of 2,4-D in water samples using the biosensor correlated well with a HPLC method.