Tajamal Hussain

Molecularly Imprinted Nanomaterials for Sensor Applications

Molecular imprinting is a well-established technology to mimic antibody-antigen interaction in a synthetic platform. Molecularly imprinted polymers and nanomaterials usually possess outstanding recognition capabilities. Imprinted nanostructured materials are characterized by their small sizes, large reactive surface area and, most importantly, with rapid and specific analysis of analytes due to the formation of template driven recognition cavities within the matrix. The excellent recognition and selectivity offered by this class of materials towards a target analyte have found applications in many areas, such as separation science, analysis of organic pollutants in water, environmental analysis of trace gases, chemical or biological sensors, biochemical assays, fabricating artificial receptors, nanotechnology, etc. We present here a concise overview and recent developments in nanostructured imprinted materials with respect to various sensor systems, e.g., electrochemical, optical and mass sensitive, etc. Finally, in light of recent studies, we conclude the article with future perspectives and foreseen applications of imprinted nanomaterials in chemical sensors.

Effect of crosslinker feed content on catalaytic activity of silver nanoparticles fabricated in multiresponsive microgels

We investigated the effect of crosslinking density of poly(N-isopropyl acrylamide-co-acrylic acid) microgels on catalytic activity of silver nanoparticles fabricated hybrid microgels. Multiresponsive poly(N-isopropyl acrylamide-co-acrylic acid) microgels with 2, 4, 6 and 8 mole percentage of N,N-methylene-bis-acrylamide were synthesized by emulsion polymerization. These microgels were characterized by dynamic light scattering and were used as microreactors to synthesize silver nanoparticles. Hybrid system was characterized by ultraviolet-visible spectroscopy. The catalytic activity of hybrid microgels with different crosslinker content was compared by studying the reduction of pnitrophenol as a model reaction. Kinetics of reaction was monitored by spectrophotometry. The value of the apparent rate constant decreases from 0.568 to 0.313min−1, when content of crosslinker are increased from 2 to 8 mole percentage respectively. This decreases in value of apparent rate constant is due to increase in diffusional barrier offered by high crosslinking of polymer network at high mole percentages of N,N-methylene-bis-acrylamide.

On Refining the Relationship between Aspect Ratio and Percolation Threshold of Practical Carbon Nanotubes/Polymer Nanocomposites

Four different aspect ratio (AR) based multiwall carbon nanotube (MWNT)/thermoplastic elastomer (TPE) polymer nanocomposites were fabricated by melt blending. In contrast to proposed mathematical models, electrical percolation thresholds of resulting nanocomposites displayed an oscillating, non-monotonic relation with increase in AR. Experimental results suggested that mathematically calculated nominal AR of MWNT was an unclear parameter to predict the percolation threshold of polymer nanocomposites. Instead, a more clear approach taking into consideration the diameter and length of nanotubes individually rather as a combined parameter of AR explained fairly well the relation between MWNT dimensions and percolation threshold.

Influence of carbon nanotube dimensions on the percolation characteristics of carbon nanotube/polymer composites

The effect of carbon nanotube aspect ratio (AR) on the percolation characteristics of their polymer composites was investigated by melt blending the multi-wall carbon nanotubes (MWCNTs) with different AR with a thermoplastic elastomer. Previously, most studies reported the effect of aspect ratio of MWCNTs only in the context of achieving the maximum electrical conductivity at lower percolation thresholds in the polymer composites. In this study, our results indicate that aspect ratio can also influence other percolation properties such as the pre-percolation conductivity, percolation conductivity and post-percolation conductivity, shape of the percolation curve, and the width of the insulator-conductor transition. We have established that AR can be used to tailor the percolation curves from sharp to quasi-linear ones, which can help us fabricate the percolative composites with stable electrical properties. Experimental results suggested that the mathematically calculated nominal AR of the MWCNTs was an un...

Phragmites karka as a Biosorbent for the Removal of Mercury Metal Ions from Aqueous Solution: Effect of Modification

Batch scale studies for the adsorption potential of novel biosorbent Phragmites karka (Trin), in its natural and treated forms, were performed for removal of mercury ions from aqueous solution. The study was carried out at different parameters to obtain optimum conditions of pH, biosorbent dose, agitation speed, time of contact, temperature, and initial metal ion concentration. To analyze the suitability of the process and maximum amount of metal uptake, Dubinin-Radushkevich (D-R) model, Freundlich isotherm, and Langmuir isotherm were applied. The values of for natural and treated biosorbents were found at 1.79 and 2.27 mg/g, respectively. The optimum values of contact time and agitation speed were found at 50 min and 150 rpm for natural biosorbent whereas 40 min and 100 rpm for treated biosorbent, respectively. The optimum biosorption capacities were observed at pH 4 and temperature 313 K for both natural P. karka and treated P. karka. values indicate that comparatively treated P. karka was more feasible for mercury adsorption compared to natural P. karka. Both pseudo-first-order and pseudo-second-order kinetic models were applied and it was found that data fit best to the pseudo-second-order kinetic model. Thermodynamic studies indicate that adsorption process was spontaneous, feasible, and endothermic.

Developing imprinted polymer nanoparticles for the selective separation of antidiabetic drugs.

In this study, new molecularly imprinted polymer (MIP) nanoparticles are designed for selective recognition of different drugs used for the treatment of type 2 diabetes mellitus, i.e. sitagliptin (SG) and metformin (MF). The SG- and MF-imprinted polymer nanoparticles are synthesized by free-radical initiated polymerization of the functional monomers: methacrylic acid and methyl methacrylate; and the crosslinker: ethylene glycol dimethacrylate. The surface morphology of resultant MIP nanoparticles is studied by atomic force microscopy. Fourier transform infrared spectra of MIP nanoparticles suggest the presence of reversible, non-covalent interactions between the template and the polymer. The effect of pH on the rebinding of antidiabetic drugs with SG- and MF-imprinted polymers is investigated to determine the optimal experimental conditions. The molecular recognition characteristics of SG- and MF-imprinted polymers for the respective drug targets are determined at low concentrations of SG (50-150 ppm) and MF (5-100 ppm). In both cases, the MIP nanoparticles exhibit higher binding response compared to non-imprinted polymers. Furthermore, the MIPs demonstrate high selectivity with four fold higher responses toward imprinted drugs targets, respectively. Recycled MIP nanoparticles retain 90% of their drug-binding efficiency, which makes them suitable for successive analyses with significantly preserved recognition features.

A miniaturized electronic sensor for instant monitoring of ethanol in gasohol fuel blends

Gasoline–ethanol (gasohol) fuel blends have gained considerable attention in the petroleum and energy sectors as relatively cheaper and greener high-octane alternative fuels with gasoline-comparable efficiency in modern transportation vehicles. However, due to different combustion rates the relative concentration of ethanol in gasohol fuel blends may vary over time. Furthermore, there is a need to monitor ethanol concentration in fuel blends for quality control applications. This article reports a miniaturized electronic sensor based on an interdigital capacitor (IDC) as the transducer and a dual-imprinted titania–polyaniline composite film as the receptor. The device has an active surface area of 0.9 cm2 and is easy to fabricate. The receptor material is synthesized by imprinting ethanol in both titania sol (EITS, the matrix) and polyaniline nanoparticles (EIPani, the filler), and subsequently mixing them to obtain a dual-imprinted EITS–EIPani composite. The structural and morphological characteristics of the receptor layers are determined with Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM), respectively. The IDC devices are fabricated with pristine EITS and dual-imprinted EITS–EIPani composite to test their metrological sensor characteristics in standard ethanol solutions and real-time gasohol fuel blends. The instant shift in capacitance is measured upon exposure to different concentrations of ethanol. These devices show excellent sensitivity and selectivity patterns and demonstrate reliable sensor response toward ethanol in different gasohol fuel blends with 1–10 vol% ethanol. The results of this study reveal that these miniaturized ethanol sensors are potentially useful for rapid analysis of ethanol in gasohol and may be optimized for onboard fuel quality control applications.

Surfactant Incorporated Co Nanoparticles Polymer Composites with Uniform Dispersion and Double Percolation

Series of Cobalt nanoparticles incorporated polymethylmethacrylate composites in the presence and absence of dodecyl-benzene-sulphonic acid (DBSA-CoNPs/PMMA and CoNPs/PMMA, resp.) were synthesized by solution mixing methodology. UV-visible and FTIR techniques were used to confirm the formation of nanocomposite. UV-visible spectra of the composites showed the incorporation of filler particles in the polymer matrix. On the other hand, FTIR spectra indicated the physical interaction between the two phases of the composite. Moreover, the electrical nature of the composites was studied by plotting graphs between electrical conductivity (measured using LCR meter at 100 kHz) and contents of the filler particles as introduced in the polymer matrix. An increase in electrical conductivity was first observed with increasing filler concentration up to the critical percolation threshold value (0.5% for DBSA-CoNPs/PMMA and 1% for CoNPs/PMMA), which then dropped upon further increments in the filler content. However, at higher concentrations, a second jump in the conductivity was observed in case of DBSA-CoNPs/PMMA composites.

Tailoring Imprinted Titania Nanoparticles for Purines Recognition

Molecular imprinted titania nanoparticles were developed for selective recognition of purines, for example, guanine and its final oxidation product uric acid. Titania nanoparticles were prepared by hydrolysis of titanium butoxide as precursor in the presence of pattern molecules. The morphology of synthesized nanoparticles is evaluated by SEM images. Recognition characteristics of imprinted titania nanoparticles are studied by exposing them to standard solution of guanine and uric acid, respectively. The resultant change in their concentration is determined by UV/Vis analysis that indicated imprinted titania nanoparticles possess high affinity for print molecules. In both cases, nonimprinted titania is taken as control to observe nonspecific binding interactions. Cross sensitivity studies suggested that imprinted titania is at least five times more selective for binding print molecules than competing analyte thus indicating its potential for bioassay of purines.

Fabrication of Ag and Ni Nanocatalyst with Enhanced Efficiency

Metal nanoparticles (NPs) have received significant attention in last decade because of their unique properties. In this work, two different metal NPs have been prepared and their catalytic activities are compared with conventional catalyst. In first case, Ag NPs were synthesized by chemical reduction method in ethanolic medium. Synthesized Ag NPs were characterized by scanning electron microscope (SEM) images which indicated an average particle size of Ag around 250 nm. The catalytic activity of Ag NPs was investigated for the oxidative mineralization of methylene blue dye. Comparative studies suggested that Ag NPs possess enhanced catalytic activity compared to bulk Ag. In second approach, supported Ni NPs were fabricated using Al2O3 as supporting surface; that is, Ni NPs get adsorbed on Al2O3 through in situ reduction reaction. Oxidative degradation of methylene blue indicated that catalytic activity of supported Ni/Al2O3 is about five times higher than simple Ni as catalyst.