Adnan Mujahid

Chemical Sensors Based on Molecularly Imprinted Sol-Gel Materials †

The sol-gel technique is earning the worldwide attention of researchers in the field of material science, due to its versatility in synthesizing inorganic ceramic materials at mild conditions. High purity, homogeneity, controlled porosity, stable temperature and nanoscale structuring are the most remarkable features offered by this method for generating highly sensitive and selective matrices to incorporate analyte molecules. The crafting of sol-gel sensors through molecular imprinting has put great influence on the development of innovative chemical sensors, which can be seen from the growing number of publications in this field. The review provides a brief overview of sol-gel sensor applications, and discusses the contribution of molecular imprinting in exploring the new world of sensors.

Advanced vapor recognition materials for selective and fast responsive surface acoustic wave sensors: A review

The necessity of selectively detecting various organic vapors is primitive not only with respect to regular environmental and industrial hazard monitoring, but also in detecting explosives to combat terrorism and for defense applications. Today, the huge arsenal of micro-sensors has revolutionized the traditional methods of analysis by, e.g. replacing expensive laboratory equipment, and has made the remote screening of atmospheric threats possible. Surface acoustic wave (SAW) sensors - based on piezoelectric crystal resonators - are extremely sensitive to even very small perturbations in the external atmosphere, because the energy associated with the acoustic waves is confined to the crystal surface. Combined with suitably designed molecular recognition materials SAW devices could develop into highly selective and fast responsive miniaturized sensors, which are capable of continuously monitoring a specific organic gas, preferably in the sub-ppm regime. For this purpose, different types of recognition layers ranging from nanostructured metal oxides and carbons to pristine or molecularly imprinted polymers and self-assembled monolayers have been applied in the past decade. We present a critical review of the recent developments in nano- and micro-engineered synthetic recognition materials predominantly used for SAW-based organic vapor sensors. Besides highlighting their potential to realize real-time vapor sensing, their limitations and future perspectives are also discussed.

Solvent Vapour Detection with Cholesteric Liquid Crystals—Optical and Mass-Sensitive Evaluation of the Sensor Mechanism

Cholesteric liquid crystals (CLCs) are used as sensitive coatings for the detection of organic solvent vapours for both polar and non-polar substances. The incorporation of different analyte vapours in the CLC layers disturbs the pitch length which changes the optical properties, i.e., shifting the absorption band. The engulfing of CLCs around non-polar solvent vapours such as tetrahedrofuran (THF), chloroform and tetrachloroethylene is favoured in comparison to polar ones, i.e., methanol and ethanol. Increasing solvent vapour concentrations shift the absorbance maximum to smaller wavelengths, e.g., as observed for THF. Additionally, CLCs have been coated on acoustic devices such as the quartz crystal microbalance (QCM) to measure the frequency shift of analyte samples at similar concentration levels. The mass effect for tetrachloroethylene was about six times higher than chloroform. Thus, optical response can be correlated with intercalation in accordance to mass detection. The mechanical stability was gained by combining CLCs with imprinted polymers. Therefore, pre-concentration of solvent vapours was performed leading to an additional selectivity.

Dual and tetraelectrode QCMs using imprinted polymers as receptors for ions and neutral analytes

Polymers as coating materials were combined with quartz crystal microbalances (QCMs) to design sensor devices for the detection of both ionic and neutral analytes in liquid phase. The design and geometry of dual and tetraelectrode QCMs have been optimized to reduce electric field interferences. An unusual Sauerbrey effect was observed while exposing potassium salt solution to 10- and 20-MHz QCMs, i.e. increase in the frequency shifts by a factor of seven, which is attributed to electro-acoustic phenomena. Non-functionalized sol-gel materials were synthesized by templating with hydrophobic salt such as tetraethyl ammonium picrate. Imprinting with these ions of low charge density leads to sensitive layers, and UV–Vis spectroscopy was used to check re-inclusion of this analyte. In the next strategy, functionalized polyurethane for potassium ions and sol-gel materials with aminopropyl group as ligand were generated to tune selectivity and sensitivity towards Ni2+ and Cu2+. Methacrylic acid polymers were optimized for the detection of atrazine by hydrogen bonding; double molecular imprinted polyurethane approach was followed for pyrene recognition. Finally, these imprinted polymers were combined with tetraelectrode QCM to develop sensor platform.

Bioimprinting strategies: From soft lithography to biomimetic sensors and beyond

Imprinting is a straightforward, yet a reliable technique to develop dynamic artificial recognition materials-so called as synthetic antibodies. Surface imprinting strategies such as soft lithography allow biological stereotyping of polymers and sol-gel phases to prepare extremely selective receptor layers, which can be combined with suitable transducer systems to develop high performance biomimetic sensors. This article presents an overview of the remarkable technical advancements in the field of surface bioimprinting with particular emphasis on surface imprinted bioanalyte detection systems and their applications in rapid bioanalysis and biotechnology. Herein, we discuss a variety of surface imprinting strategies including soft lithography, template immobilization, grafting, emulsion polymerization, and others along with their biomimetic sensor applications, merits and demerits. The pioneering research works on surface patterned biosensors are described with selected examples of detecting biological agents ranging from small biomolecules and proteins to living cells and microorganisms.

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.

Monitoring automotive oil degradation: analytical tools and onboard sensing technologies.

AbstractEngine oil experiences a number of thermal and oxidative phases that yield acidic products in the matrix consequently leading to degradation of the base oil. Generally, oil oxidation is a complex process and difficult to elucidate; however, the degradation pathways can be defined for almost every type of oil because they mainly depend on the mechanical status and operating conditions. The exact time of oil change is nonetheless difficult to predict, but it is of great interest from an economic and ecological point of view. In order to make a quick and accurate decision about oil changes, onboard assessment of oil quality is highly desirable. For this purpose, a variety of physical and chemical sensors have been proposed along with spectroscopic strategies. We present a critical review of all these approaches and of recent developments to analyze the exact lifetime of automotive engine oil. Apart from their potential for degradation monitoring, their limitations and future perspectives have also been investigated. FigureOnboard assessment of oil quality: the sensors and spectroscopic strategies proposed for this are reviewed

Imprinted sol–gel materials for monitoring degradation products in automotive oils by shear transverse wave

Titania sol-gel layers imprinted with capric acid have been used as synthetic receptors for highly sensitive detection of oxidized products resulting from degradation of automotive engine oil. These layers have been applied as sensitive coating material on shear transverse wave (STW) resonators of frequencies ranging from 100 MHz to 430 MHz. A relatively small size of STW resonators, i.e. about 2 mm for 430 MHz makes these devices extremely useful while considering the concept of miniaturization. It has been proved experimentally that by increasing fundamental resonance frequency of these devices, a very high sensor response i.e. 22 kHz up to 460 kHz can be generated. The geometry of long chain capric acid fits best as recognition element in the synthesis of imprinted TiO(2) network. The thin titania layers coated on transducer surface provide excellent diffusion pathways to oxidized products of waste engine oil for selective and reversible re-inclusion i.e. recovery time of 30 min. Viscosity effects of oxidized engine oil can be minimized by shear waves which do not dissipate considerable amount of energy that ensure smooth liquid phase operation. Different oxidized products i.e. carbonic acids and esters can be characterized in lubricant via infra-red (IR) spectroscopy. The increasing IR absorbance of different waste oil samples is a clear indication of increasing concentration of carbonyl group. The IR absorbance of carbonyl groups is directly correlated to the age of respective waste engine oil samples and a quantitative relationship between sensor responses from STWs and IR absorbance was also developed.

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...

Blood Group Typing: From Classical Strategies to the Application of Synthetic Antibodies Generated by Molecular Imprinting

Blood transfusion requires a mandatory cross-match test to examine the compatibility between donor and recipient blood groups. Generally, in all cross-match tests, a specific chemical reaction of antibodies with erythrocyte antigens is carried out to monitor agglutination. Since the visual inspection is no longer useful for obtaining precise quantitative information, therefore there is a wide variety of different technologies reported in the literature to recognize the agglutination reactions. Despite the classical methods, modern biosensors and molecular blood typing strategies have also been considered for straightforward, accurate and precise analysis. The interfacial part of a typical sensor device could range from natural antibodies to synthetic receptor materials, as designed by molecular imprinting and which is suitably integrated with the transducer surface. Herein, we present a comprehensive overview of some selected strategies extending from traditional practices to modern procedures in blood group typing, thus to highlight the most promising approach among emerging technologies.