Bhim Bali Prasad

Molecularly imprinted polymer-based solid-phase microextraction fiber coupled with molecularly imprinted polymer-based sensor for ultratrace analysis of ascorbic acid.

Clinical manifestations owing to ascorbic acid deficiency demand an easy-to-use, rapid, robust and inexpensive technique, which can measure serum ascorbic acid at ultratrace level to attend the problem of hypovitaminosis C and acute cases of scurvy. In the present work, a novel molecularly imprinted polymer (MIP)-coated solid-phase microextraction (SPME) fiber that could be coupled to a complementary MIP-sensor was prepared with ascorbic acid as a template molecule. The characteristics and applications of this fiber were investigated. The same MIP receptor for both SPME and the corresponding sensor was able to enhance the preconcentration of analyte substantially so as to attain the stringent level of sensitivity in highly diluted aqueous, blood serum and pharmaceutical samples. The extraction yield of ascorbic acid (AA) with the MIP-coated fiber was found to be quantitative (detection limit 0.0396 ng mL(-1), RSD=2.3%, S/N=3) in aqueous samples without any problem of non-specific false positive results and cross-reactivity.

Creatinine sensor based on a molecularly imprinted polymer-modified hanging mercury drop electrode

Molecularly imprinted polymers (MIP) have been elucidated to work as artificial receptors. In our present study, a MIP was applied as a molecular recognition element to a chemical sensor. We have constructed a creatinine sensor based on a MIP layer selective for creatinine and its differential pulse, cathodic stripping voltammetric detection (DPCSV) on a hanging mercury drop electrode (HMDE). The creatinine sensor was fabricated by the drop coating of dimethylformamide (DMF) solution of a creatinine-imprinted polymer onto the surface of HMDE. The modified-HMDE, preanodised in neutral medium at +0.4V versus Ag/AgCl for 120s, exhibited a marked enhancement in DPCSV current in comparison to the less anodised (</=+0.3V) HMDE. The creatinine was preconcentrated and instantaneously oxidised in MIP layer giving DPCSV response in the concentration range of 0.0025-84.0mugmL(-1) [detection limit (3sigma) 1.49ngmL(-1)]. The sensor was found to be highly selective for creatinine without any response of interferents viz., NaCl, urea, creatine, glucose, phenylalanine, tyrosine, histidine and cytosine. The non-imprinted polymer-modified electrode did not show linear response to creatinine. The imprinting factor as high as 9.4 implies that the imprinted polymer exclusively acts as a recognition element of creatinine sensor. The proposed procedure can be used to determine creatinine in human blood serum without any preliminary treatment of the sample in an accurate, rapid and simple way.

Development of a highly sensitive and selective hyphenated technique (molecularly imprinted micro-solid phase extraction fiber-molecularly imprinted polymer fiber sensor) for ultratrace analysis of folic acid.

A simple polymerization strategy is reported in this work which allows molecularly imprinted polymeric fiber (monolith) fabrication for direct use in sensing devices. This is advantageous for achieving higher degree of enrichment of target analyte (folic acid) from the complex matrices of real samples, without any surface fouling, cross-reactivity, and non-specific (false-positive) contributions. In order to measure serum folic acid at ultratrace level to detect spina bifida, a neural tube defect in mother, and other acute cases of proteomic diseases, the hyphenation between molecularly imprinted micro-solid phase extraction fiber and a complementary molecularly imprinted polymer-carbon composite fiber sensor has been found quite efficient. The primitive diagnosis of many chronic diseases is feasible by estimating folic acid as biomarker, with the detection limit as low as 0.0036 ng mL(-1) (relative standard deviation=0.13%, signal/noise=3) in human blood serum.

Enatioselective quantitative separation of d- and l-thyroxine by molecularly imprinted micro-solid phase extraction silver fiber coupled with complementary molecularly imprinted polymer-sensor

Thyroxine is a known disease biomarker which demands a highly sensitive and selective technique to measure ultratrace level with enantiodifferentiation of its optical isomers (d- and l-), in real samples. In this work, an approach of hyphenation between molecularly imprinted micro-solid phase extraction and a complementary molecularly imprinted polymer-sensor was adopted for enantioseparation, preconcentration, and analysis of d- and l-thyroxine. In both techniques, the same imprinted polymer, coated on a vinyl functionalized self-assembled monolayer modified silver wire, was used as the respective extraction fiber as well as sensor material. This combination enabled enhanced preconcentration of test analyte substantially so as to achieve the stringent limit [limit of detection: 0.0084 ng mL(-1), RSD=0.81%, S/N=3 (d-thyroxine); 0.0087 ng mL(-1), RSD=0.63%, S/N=3 (l-thyroxine)] of clinical detection of thyroid-related diseases, without any problems of non-specific false-positive contribution and cross-reactivity.

Doubly imprinted polymer nanofilm-modified electrochemical sensor for ultra-trace simultaneous analysis of glyphosate and glufosinate

A rapid, selective, and sensitive double-template imprinted polymer nanofilm-modified pencil graphite electrode was fabricated for the simultaneous analysis of phosphorus-containing amino acid-type herbicides (glyphosate and glufosinate) in soil and human serum samples. Since both herbicides respond overlapped oxidation peaks and only glyphosate is prone to nitrosation, n-nitroso glyphosate and glufosinate were used as templates for obtaining the well-resolved quantitative differential pulse anodic stripping voltammetric peaks on the proposed sensor. Toward sensor fabrication, a nano-structured polymer film was first grown directly on the electrode via initial immobilization of gold nanoparticles at its surface. This was followed by linking of monomeric (N-methacryloyl-l-cysteine) molecules through S-Au bonds. Subsequently, these molecules were subjected to free radical polymerization, in the presence of templates, cross linker, initiator, and multiwalled carbon nanotubes as pre-polymer mixture. The modified sensor observed wide linear ranges (3.98-176.23 ng mL(-1) and 0.54-3.96 ng mL(-1)) of simultaneous analysis with detection limits as low as 0.35 and 0.19 ng mL(-1) (S/N=3) for glyphosate and glufosinate, respectively, in aqueous samples. The respective oxidation peak potentials of both analytes were found to be substantially apart by 265 mV. This enabled the simultaneous determination of one target in the presence of other, without any cross reactivity, interferences, and false-positives, in real samples.

Metal ion mediated imprinting for electrochemical enantioselective sensing of L-histidine at trace level.

Enantioselective trace level sensing of l-histidine (limit of detection, 1.980 ngm L(-1), S/N=3) was feasible with the use of a typical, reproducible, and rugged complex imprinted polymer-based pencil graphite electrode, in aqueous samples. In the present instance, the Cu(2+) ion-mediated imprinting of l-histidine in an molecularly imprinted polymer motif actually helped upbringing electrocatalytic activity to respond an enhanced differential pulse anodic stripping voltammetric oxidation peak of l-histidine, without any cross-reactivity and false-positive, in real samples. The proposed sensor could be considered suitable for the practical applications in biomarking histedinemia, a disease associated with L-histidine metabolic disorders, in clinical settings.

Enantioselective recognition of d- and l-tryptophan by imprinted polymer-carbon composite fiber sensor

Electrochemical sensors demonstrating enantioselectivity to tryptophan enantiomers, with high selectivity and sensitivity, were fabricated by the use of a monolithic fiber of molecularly imprinted polymer-carbon composite. The recognition mechanism and performance of these sensors were evaluated by differential pulse anodic stripping voltammetry. The sensor imprinted for l-tryptophan not only discriminated the target from its analogues and other amino acids but also responded specifically in racemic mixture in aqueous, biological, and pharmaceutical samples. The binding kinetics of L-tryptophan was also established with the help of anodic stripping cyclic voltammetry and chronocoulometry. The detection limit for L-tryptophan was as low as 0.24 ng mL(-1) (signal/noise=3) which is appropriate for biomarking diseases, caused by an acute tryptophan-depletion, in clinical setting.

Study on monomer suitability toward the template in molecularly imprinted polymer: an ab initio approach.

Study of monomer-template interactions in molecularly imprinted polymer (MIP) is inevitable to comprehend best selectivity at the molecular level in pre-polymer solution. In the present work, binding energies of tryptophan, an amino acid template, complexed with different monomers were computed using second order Moller Plesset theory (MP2) at 6-311++g** level in gas phase. This helped in recommending a generic MIP, suitable for the selective and sensitive diagnosis of tryptophan, in clinical setting as disease biomarker, at primitive level. The tryptophan is an important biomarker owing to its highly regulated physiological process in the treatment of premenstrual dysphoric disorder and pellagra like diseases. Frequency calculations were performed using Density Functional Theory (DFT) at B3LYP employing 6-31+g (2d, 2p) level including thermal and entropy corrections. The monomer, p-nitrophenyl acrylate (2 mol), was adjudged having giving best binding score for the complexation at ground state with tryptophan (1 mol) for MIP development.

A dual-ion imprinted polymer embedded in sol-gel matrix for the ultra trace simultaneous analysis of cadmium and copper.

In simultaneous determination of group of elements, there are inter-metallic interactions which result in a non-linear relationship between the peak current and ionic concentration for each of the element, at bare (unmodified) electrode. To resolve this problem, we have resorted, for the first time, to develop a modified pencil graphite electrode using a typical ion imprinted polymer network (dual-ion imprinted polymer embedded in sol-gel matrix (inorganic-organic hybrid nano-material)) for the simultaneous analysis of a binary mixture of Cd(II) and Cu(II) ions, without any complication of inter-metallic interactions and competitive bindings, in real samples. The adequate resolution of differential pulse anodic stripping voltammetry peaks by 725 mV (cf, 615 mV with unmodified electrode), without any cross-reactivity and the stringent detection limits as low as, 0.050 and 0.034 ng mL(-1) (S/N=3) for Cd(II) and Cu(II) ions, respectively by the proposed sensor can be considered useful for the primitive diagnosis of several chronic diseases in clinical settings.

Preparation, characterization and performance of a silica gel bonded molecularly imprinted polymer for selective recognition and enrichment of β-lactam antibiotics

Abstract A silica gel-bound molecularly imprinted polymer to oxazolone(s) exclusively derived from certain cephalosporins (cefaclor) and penicillins (amoxycillins and ampicillins) was prepared using ethylacetate as a porogen. This was used as a packing material for solid phase extraction in column chromatography. The high selectivity and the quantitative sorption of oxazolone at pH 7.5 and a flow rate of 5.0 ml min−1 in a long (13.0 cm) and wide bore (1.4 cm internal diameter) column have led to efficient clean-up, selective enrichment, and indirect differential pulse adsorptive stripping voltammetric measurement of the β-lactams in the form of corresponding oxazolones either in a larger volume of dilute aqueous systems or in the pharmaceutical formulations, without complications of complex matrices, excipients or column deterioration.