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Herein, we report a facile approach for constructing a calixarene-based electrochemical heavy metal sensor (Calix/MPA/Au) via a one-pot reaction for the detection of Ni(II) and Zn(II) ions. The surface elemental properties and analytical performance of the Calix/MPA/Au sensor were characterized by X-ray photoelectron spectroscopy (XPS) and differential pulse voltammetry (DPV). Under optimum conditions, the sensor exhibited detection limits of 1.5 and 0.34 mg/L at linear ranges of 2.85–6.65 and 0.13–1.68 mg/L for the Zn(II) and Ni(II) ions, respectively. The developed sensor exhibited a better electrochemical performance in the detection of Zn(II) and Ni(II) ions owing to the favourable host–guest interactions between the hydroxyl groups-functionalized lower rim of dicarboxyl-calix[4]arene and the metal ions. The RSD of the five independent Calix/MPA/Au electrode for Zn(II) and Ni(II) ions was calculated to be 16.3 and 16.1%, respectively. Despite the lower sensitivity of the modified electrode towards Ni(II) ions, this finding proves the high selectivity of the calixarene as a detection probe towards the fitted size of guest ion, hence promising to be assembled and explored as a solid-state based-supramolecular host molecule for tracing metal ions.

Calix[4]arene-polyurethane (C4PU) polymer was used as an alternative adsorbent for the adsorption of methylene blue (MB) and malachite green (MG) dyes, from the aqueous solution. C4PU was synthesised by reacting p-tert-butyl calix[4]arene with hexamethylene diisocyanate (HMDI) as the cross-linking agent. A preliminary study was carried out to determine the best ratio of calix[4arene and HMDI in the adsorption of dyes and C4PU-4 shows a better adsorption compared to the synthesized C4PU in other ratios. The polymer was characterised by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) analysis and point of zero charge (pHPZC). The isotherms and kinetics of the adsorption of MB and MG were studied under a range of experimental conditions, including pH, adsorbent dosage, initial dye concentration, and contact time. The adsorption was determined by the adsorption percentage of MB and MG dyes from the solution. The adsorption process for both dyes is best described by the Langmuir isotherm model, and it follows the pseudo-second order kinetic model, with the maximum adsorption capacity (qmax) of MB and MG, respectively, was found to be 1.619 mg.g− 1 and 2.192 mg.g− 1.

In this work, an electrochemical sensor for anthracene detection was constructed based on a modified electrode consisting of thiolated calixarene (TC4)-functionalized gold nanoparticles (AuNPs) and electrochemically reduced graphene oxide (ERGO). Firstly, graphene oxide GO) was reduced on screen printed carbon electrodes (SPCE), followed by the immobilization of AuNPs and TC4 through a self-assembly process to form TC4/AuNPs/ERGO-SPCE. The molecules’ structure was characterized using FTIR and Raman spectroscopy, the sample’s morphology and topology were characterized using Field Emission Scanning Electron Microscopy (FESEM), High Resolution Transmission Electron Microscopy (HRTEM) and electrochemical performance of developed sensor was characterized using electrochemical method. Owing to the outstanding supramolecular recognition of anthracene by TC4, the target analyte was detected accurately with a linear range of 1- $7~\mu \text{M}$ and limit of detection down to $0.0625~\mu \text{M}$ (S/N = 3). Additionally, the sensor was acknowledged for its excellent anti-interference properties in the presence of organic compounds as well as inorganic metal ions. The proposed sensor also yielded comparable results to conventional HPLC method, with a satisfactory recovery of 92–98% in environmental samples.

The past several decades have seen increasing concern regarding the wide distribution of polycyclic aromatic hydrocarbons (PAHs) in environmental matrices. Primary toxicological data show PAHs' persistent characteristics and possible toxicity effects. Because of this pressing global issue, electroanalytical methods have been introduced. These methods are effective for PAH determination in environmental waters, even outclassing sophisticated analytical techniques such as chromatography, conventional spectrophotometry, fluorescence, and capillary electrophoresis. Herein, the literature published on PAHs is reviewed and discussed with special regard to PAH occurrence. Moreover, the recent developments in electrochemical sensors for PAH determination and the challenges and future outlooks in this field, are also presented.

This study generally classifies air pollutants on the basis of: primary or secondary, natural or anthropogenic, chemical composition, physical state, and the space scales of their effects. Air pollutants that affect air quality in Nigeria were discussed based on natural and anthropogenic sources. The natural sources include: sand dust, sea spray, volcanic activities, smoke and carbon monoxide from wildfires among others, while the anthropogenic sources include: vehicular emissions, mining activities, industries such as cement companies and quarry factories, agricultural practices and solid waste dumps among others. Some of the atmospheric pollutants that posed greatest threat to human health were equally examined. They include: Sulphur dioxide (SO2) which can react with water vapor (H2O) in the atmosphere to form sulphuric acid (H2SO4) and thus acid rain; particulate matter (PM) with less than 10 μm, particularly fine particles (PM2.5 ) and particles in the fine fraction that are smaller than 0.1 μm (ultrafine particles), can carry toxic chemicals which are linked to cancer; carbon monoxide (CO), even in very small concentrations, can prevent oxygen from being delivered through the body major organs; ozone which is a highly reactive gas causes oxidation of a number of macromolecules within a biological system and produces free radicals that can damage DNA molecules and cause carcinogenesis. Based on the aforementioned, this study recommends that priority should be given to the establishment of air monitoring stations in all urban centers of the country in order to provide accurate and continuous information on air quality. Keywords: anthropogenic pollutants, atmosphere, particulate matter, pollution

In this study, enhancement of electrochemical performance of electrochemically reduced graphene oxide (ERGO) on a screen-printed carbon electrode (SPCE) (ERGO/SPCE) coupled with ion-pairing (cetyltrimethylammonium bromide, CTAB) for the determination of iodide in table salt has been described. The electrode modification of ERGO/SPCE was conducted using cyclic voltammetric (CV) scanning in the potential range of 1.3-0.4 V for 50 cycles after the drop-casting of graphene oxide (GO) suspension on the SPCE. It was found that the electro-active surface area of ERGO/SPCE was increased by 1.5-fold compared to the bare SPCE. ERGO/SPCE sensor displays linearity towards iodide in the concentration range from 0.020 to 1.0 mg/L (sensitivity = 5.40 µA(mg/L)

A portable electrochemical aptamer-antibody based sandwich biosensor has been designed and successfully developed using an aptamer bioreceptor immobilized onto a screen-printed electrode surface for Mycobacterium tuberculosis (M. tuberculosis) detection in clinical sputum samples. In the sensing strategy, a CFP10-ESAT6 binding aptamer was immobilized onto a graphene/polyaniline (GP/PANI)-modified gold working electrode by covalent binding via glutaraldehyde linkage. Upon interaction with the CFP10-ESAT6 antigen target, the aptamer will capture the target where the nano-labelled Fe3O4/Au MNPs conjugated antibody is used to complete the sandwich format and enhance the signal produced from the aptamer–antigen interaction. Using this strategy, the detection of CFP10-ESAT6 antigen was conducted in the concentration range of 5 to 500 ng/mL. From the analysis, the detection limit was found to be 1.5 ng/mL, thereby demonstrating the efficiency of the aptamer as a bioreceptor. The specificity study was carried out using bovine serum albumin (BSA), MPT64, and human serum, and the result demonstrated good specificity that is 7% higher than the antibody–antigen interaction reported in a previous study. The fabricated aptasensor for M. tuberculosis analysis shows good reproducibility with an relative standard deviation (RSD) of 2.5%. Further analysis of M. tuberculosis in sputum samples have shown good correlation with the culture method with 100% specificity and sensitivity, thus making the aptasensor a promising candidate for M. tuberculosis detection considering its high specificity and sensitivity with clinical samples.

A facile electrochemical sandwich immunosensor for the detection of a breast cancer biomarker, the human epidermal growth factor receptor 2 (HER2), was designed, using lead sulfide quantum dots-conjugated secondary HER2 antibody (Ab2-PbS QDs) as a label. Using Ab2-PbS QDs in the development of electrochemical immunoassays leads to many advantages such as straightforward synthesis and well-defined stripping signal of Pb(II) through acid dissolution, which in turn yields better sensing performance for the sandwiched immunosensor. In the bioconjugation of PbS QDs, the available amine and hydroxyl groups from secondary anti-HER2 and capped PbS QDs were bound covalently together via carbonyldiimidazole (CDI) acting as a linker. In order to quantify the biomarker, SWV signal was obtained, where the Pb2+ ions after acid dissolution in HCl was detected. The plated mercury film SPCE was also detected in situ. Under optimal conditions, HER2 was detected in a linear range from 1–100 ng/mL with a limit of detection of 0.28 ng/mL. The measures of satisfactory recoveries were 91.3% to 104.3% for the spiked samples, displaying high selectivity. Therefore, this method can be applied to determine HER2 in human serum.

In this study, the synthesis and the effect of temperature and power excitation towards photoluminescence (PL) emission of colloidal PbS quantum dots (QDs) were reported. Water soluble PbS QDs capped with a mixture of 1-thioglycerol (TGL) and dithioglycerol (DTG) was synthesized via colloidal chemistry method at room temperature. The PL emission of PbS QDs was investigated under temperature range from 10 K to 300 K and we found that the PL emission blue-shifted when the temperature is increased. From high resolution transmission electron microscopy (HRTEM), the average size of PbS core QDs is determined to be 6 nm and the integrated PL intensity (IPL) versus excitation power density shows the recombination of electrons and holes occur efficiently at low and high temperature for the PbS QDs. Full width half maximum (FWHM) shows a gradual broadening with the increasing temperature due to the interaction of charge carriers with phonons.

Lead sulphide (PbS) modified with calix[6]arene was synthesised as an alternative and regenerative adsorbent for the adsorption of methylene blue (MB) dye. The prepared calix[6]arene-modified PbS was characterised via Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The response surface methodology (RSM) based on the central composite design (CCD) was employed to identify the most significant factors, such as the initial concentration, adsorbent dosage, pH, and temperature, and to optimise the effects of the factors on the adsorptive efficiency as its response. The optimised initial concentration, adsorbent dosage, pH, and temperature were 20.00 mg/L initial concentration, 44.00 mg calix[6]arene-modified PbS, pH 6, and a temperature of 31.00 &deg, C. A good correlation between the values and well-fitted model was observed. The adsorption performance was evaluated based on the percentage removal of MB dye from the water system. The adsorption isotherm best fit the Langmuir isotherm model, and the adsorption rate was followed by a pseudo-second-order kinetic model, a single layer chemical adsorption with a maximum adsorption capacity (qmax) of 5.495 mg/g.

Abstract A colourimetric assay for the detection of DNA fragments associated with the oil palm pathogen Ganoderma boninense and other fungi DNA is reported. The assay is based on the aggregation of DNA-nanoparticle conjugates in the presence of complementary DNA from the target organism. Here, various designs of DNA-nanoparticle conjugates were evaluated, and it was found that the best design gave a visually observable colour change with as little as 2 pmol of double-stranded DNA analyte even in the presence of a large excess of a mixture of non-complementary DNA. Overall, this label-free system is rapid, sensitive, selective, simple in design, and easy to carry out. It does not require specialist equipment or specialist training for the interpretation of the results, and therefore has the potential to be deployed for agricultural diagnostics in the field. Graphic abstract Development of a colourimetric assay based on DNA-nanoparticle conjugates for the oil palm pathogen Ganoderma boninense.

An early detection of Mycobacterium tuberculosis is very important to reduce the number of fatal cases and allow for fast recovery. However, the interpretation of the result from smear microscopy requires skilled personnel due to the propensity of the method to produce false-negative results. In this work, a portable, rapid, and simple sandwich-type immunosensor reader has been developed that is able to detect the presence of M. tuberculosis in sputum samples. By using sandwich-type immunosensor, an anti-CFP10-ESAT6 antibody was immobilized onto the graphene/polyaniline (GP/PANI)-modified gold screen-printed electrode. After incubation with the target CFP10-ESAT6 antigen, the iron/gold magnetic nanoparticles (Fe3O4/Au MNPs) conjugated with anti-CFP10-ESAT6 antibody were used to complete the sandwich format. Differential pulse voltammetry (DPV) technique was used to detect the CFP10-ESAT6 antigen at the potential range of 0.0–1.0 V. The detection time is less than 2 h. Under optimal condition, CFP10-ESAT6 antigen was detected in a linear range from 10 to 500 ng mL−1 with a limit of detection at 1.5 ng mL−1. The method developed from this process was then integrated into a portable reader. The performance of the sensor was investigated and compared with the standard methods (culture and smear microscopy). It provides a good correlation (100% sensitivity and 91.7% specificity) with both methods of detection for M. tuberculosis in sputum samples henceforth, demonstrating the potential of the device as a more practical screening tool. Graphical abstract

Clenbuterol (CLB) is an illegal antibiotic for livestock, which is misused as a growth promoter drug. In this study, an immunosensor modified with poly(3,4-ethylenedioxythiophene) (PEDOT), multi-walled carbon nanotubes (MWCNT) and anti-clenbuterol antibody (Ab) was developed for the detection of CLB. A screen-printed carbon electrode (SPCE) was modified with PEDOT/MWCNT as a sensor platform before immobilizing Ab for specific CLB binding through a competitive-type immunoassay. Free CLB in the sample solution competed with clenbuterol-horseradish peroxide (CLB-HRP) to bind with Ab. A high current signal was obtained after optimization of the electrochemical immunoassay conditions (pH, incubation temperature, antigen (Ag) incubation time and % blocking) using the response surface methodology/central composite design (RSM/CCD). The developed immunosensor is highly reproducible and sensitive with good storage stability, which are necessary for practical application. In real sample application, this immunosensor produces comparable results with liquid chromatography-mass spectrometry; thus, it is useful for CLB screening and monitoring in real meat samples.

Nanomaterial-enabled electrochemical sensors are designed as an economical, efficient, and user-friendly analytical tool for on-site and routine nitrate analysis over a wide range of environmental samples. The remarkable advances and tunable attributes of nanomaterials have greatly improved the analytical performance of electrochemical nitrate sensors. In this review, a comprehensive elucidation of the recent advances in nanomaterial-based electrochemical nitrate sensors is presented. The review firstly provides a general introduction, followed by typical electrochemical sensing methods. The next two sections detail various nanomaterials, including graphene derivatives, carbon nanotubes/fibers, metal/bimetal/metal oxide nanoparticles, and conducting polymers for modifying electrodes in enzymatic and non-enzymatic electrochemical nitrate sensors. Finally, the perspectives and current challenges in achieving real-world applications of nanomaterial-based electrochemical nitrate sensors are outlined.

The Box-Behnken design (BBD) approach was used in this work for the optimization of electropolymerization of poly(3,4-ethylenedioxythiophene) (PEDOT) with graphene oxide (GO) to yield high peak current response. The concentration of GO, electropolymerization potential and deposition time were investigated by response surface methodology (RSM). The interaction between these factors was studied and modeled to identify the significant and most influential parameters. The statistical analysis showed that concentration of GO, electropolymerization potential and deposition time had significant effects on the peak current response. The model was able to predict the peak current response with

A colorimetric assay for the detection of DNA fragments associated with the oil palm pathogen Ganoderma boninense is reported, which is based on the aggregation of DNA-nanoparticle conjugated in the presence of complementary DNA from the pathogen. Here, various designs of DNA-nanoparticle conjugates were evaluated, and it was found that the best design gave a visually observable colour change with as little as 2 pmol of double-stranded DNA analyte even in the presence of a large excess of a mixture of non-complementary DNA. The assay was also able to differentiate analyte sequences with three or more single nucleotide mismatches. Overall, this label-free system is rapid, sensitive, selective, simple in design and easy to carry out. It does not require specialist equipment or specialist training for the interpretation of the results and therefore has the potential to be deployed of agricultural diagnostics in the field.

There is an increasing demand for lithography methods to enable the fabrication of diagnostic devices for the biomedical and agri-food sectors. In this regard, scanning probe lithography methods have emerged as a possible approach for this purpose, as they are not only convenient, robust and accessible, but also enable the deposition of &ldquo, soft&rdquo, materials such as complex organic molecules and biomolecules. In this report, the use of polymer pen lithography for the fabrication of DNA oligonucleotide arrays is described, together with the application of the arrays for the sensitive and selective detection of Ganoderma boninense, a fungal pathogen of the oil palm. When used in a sandwich assay format with DNA-conjugated gold nanoparticles, this system is able to generate a visually observable result in the presence of the target DNA. This assay is able to detect as little as 30 ng of Ganoderma-derived DNA without any pre-amplification and without the need for specialist laboratory equipment or training.

There is an increasing demand for lithography methods to enable the fabrication of diagnostic devices for the biomedical and agri-food sectors. In this regard, scanning probe lithography methods have emerged as a possible approach for this purpose, as they are not only convenient, robust and accessible, but also enable the deposition of “soft” materials such as complex organic molecules and biomolecules. In this report, the use of polymer pen lithography for the fabrication of DNA oligonucleotide arrays is described, together with the application of the arrays for the sensitive and selective detection of Ganoderma boninense, a fungal pathogen of the oil palm. When used in a sandwich assay format with DNA-conjugated gold nanoparticles, this system is able to generate a visually observable result in the presence of the target DNA. This assay is able to detect as little as 30 ng of Ganoderma-derived DNA without any pre-amplification and without the need for specialist laboratory equipment or training.

Modification of electrode surface with poly(3,4-ethylenedioxythiophene)/multi-walled carbon nanotube (PEDOT/MWCNT) composite prepared by electrodeposition technique was reported in this study. The optimization of peak current response of PEDOT/MWCNT was performed by utilizing the combination of response surface methodology and central composite design (RSM/CCD). The effect of each variable and the interaction between three variables i.e. the concentration of MWCNT, electrodeposition potential and deposition time were studied and modeled. The statistical analysis showed that the concentration of MWCNT and deposition time have significantly affected the peak current response. A reduced cubic model equation with the coefficient of determination (R2) value of 0.9973 was developed. The optimized condition predicted by the software was compared with the experiment and resulting in less than 2% error, indicating that this model was reliable and able to predict the peak current response accurately. Additionally, the electrochemical properties, chemical properties and morphology of the optimized modified electrode were characterized by cyclic voltammetry (CV), Fourier transform infrared (FTIR), Raman spectroscopy and field emission scanning electron microscopy (FESEM). The peak current of the optimized PEDOT/MWCNT modified electrode was higher than electrode without MWCNT and the FESEM study demonstrated that the tubular structure of MWCNT was uniformly wrapped by PEDOT. The FTIR and Raman spectra proved that MWCNT was successfully incorporated into PEDOT.

This paper describes how the sensitivity of an optical DNA nanosensor based on MNPs and QDs was enhanced by using computer simulations including an innovative software, Grasshopper. The data used was derived from a previously constructed mechanism which, although successful in detecting target DNA qualitatively, raised some areas for further investigation. By adjusting the relative proportions of DNA probes, MNPs and QDs in the model, we were able to simulate a range of different reactions in the sensor and to measure them quantitatively. We were able to observe MNPs and QDs binding to more than one strand of DNA and to better understand how they network in different concentrations of the solution. We found a direct correlation coefficient of 0.9666 between the fluorescent intensity of the CdSe/ZnS QDs and the concentration of tDNA within the range of 1 × 10−6–3.9 × 10−9 M. To optimize the sensor further, we also modified the hybridization procedure, breaking it into two steps. This produced a very satisfactory LOD calculation of 1.75 × 10−9 M. Finally, when we applied the 2 step hybridization procedure we were able to improve the sensitivity of the optical nanosensor up to 20% furthur.

Although nanoparticle-enhanced biosensors have been extensively researched, few studies have systematically characterized the roles of nanoparticles in enhancing biosensor functionality. This paper describes a successful new method in which DNA binds directly to iron oxide nanoparticles for use in an optical biosensor. A wide variety of nanoparticles with different properties have found broad application in biosensors because their small physical size presents unique chemical, physical, and electronic properties that are different from those of bulk materials. Of all nanoparticles, magnetic nanoparticles are proving to be a versatile tool, an excellent case in point being in DNA bioassays, where magnetic nanoparticles are often used for optimization of the hybridization and separation of target DNA. A critical step in the successful construction of a DNA biosensor is the efficient attachment of biomolecules to the surface of magnetic nanoparticles. To date, most methods of synthesizing these nanoparticles have led to the formation of hydrophobic particles that require additional surface modifications. As a result, the surface to volume ratio decreases and nonspecific bindings may occur so that the sensitivity and efficiency of the device deteriorates. A new method of large-scale synthesis of iron oxide (Fe3O4) nanoparticles which results in the magnetite particles being in aqueous phase, was employed in this study. Small modifications were applied to design an optical DNA nanosensor based on sandwich hybridization. Characterization of the synthesized particles was carried out using a variety of techniques and CdSe/ZnS core-shell quantum dots were used as the reporter markers in a spectrofluorophotometer. We showed conclusively that DNA binds to the surface of ironoxide nanoparticles without further surface modifications and that these magnetic nanoparticles can be efficiently utilized as biomolecule carriers in biosensing devices.

In the present study, the construction of arrays on silicon for naked-eye detection of DNA dengue was demonstrated. The array was created by exposing a polyethylene glycol (PEG) silane monolayer to 254 nm ultraviolet (UV) light through a photomask. Formation of the PEG silane monolayer and photomodifed surface properties was thoroughly characterized by using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. The results of XPS confirmed that irradiation of ultraviolet (UV) light generates an aldehyde functional group that offers conjugation sites of amino DNA probe for detection of a specific dengue virus target DNA. Employing a gold enhancement process after inducing the electrostatic interaction between positively charged gold nanoparticles and the negatively charged target DNA hybridized to the DNA capture probe allowed to visualize the array with naked eye. The developed arrays demonstrated excellent performance in diagnosis of dengue with a detection limit as low as 10 pM. The selectivity of DNA arrays was also examined using a single base mismatch and noncomplementary target DNA.

N-trans feruloyltyramine amide was successfully synthesized from 4-hydroxy-3-methoxycinnamic acid and tyramine hydrochloride in a one-step lipase catalysed reaction. The use of immobilized lipase, lipozyme TL IM as the catalyst in the reaction allowed simple isolation of the enzyme from the products and other components in the reaction mixture. N-feruloyltyramine amide was characterized using Fourier Transform Infrared (FTIR) Spectroscopy, Proton Nuclear Magnetic Resonance (1H NMR) and elemental analysis. Under optimized conditions 93.5% yield was obtained when the process was carried out for 48 h using a molar ratio of cinnamic acid:tyramine HCl, 6:1 at 40°C. In addition, a rapid simple and sensitive HPLC-UV method was developed for the determination of N-feruloyltyramine using an ®Rp-8 endcapped column. The optimum mobile phase used was acetonitrile:disodium hydrogen phosphate, 30:70(v/v.). N-feruloyltyramine amide was detected at a retention time of 12 min. The calibration curve was linear over...

Using scanning near-field lithography (SNP), it is possible to pattern molecules at surfaces with a resolution as good as 9 nm [M. Montague, R. E. Ducker, K. S. L. Chong, R. J. Manning, F. J. M. Rutten, M. C. Davies and G. J. Leggett, Langmuir 23 (13), 7328–7337 (2007)]. However, in common with other scanning probe techniques, SNP has previously been considered a serial process, hindering its use in many applications. IBM’s “Millipede” addresses this problem by utilizing an array of local probes operating in parallel. Here, we describe the construction of two instruments (Snomipedes) that integrate near-field optical methods into the parallel probe paradigm and promise the integration of top–down and bottom–up fabrication methods over macroscopic areas. Both are capable of performing near-field lithography with 16 probes in parallel spanning approximately 2 mm. The instruments can work in both ambient and liquid environments, key to many applications in nanobiology. In both, separate control of writing is possible for each probe. We demonstrate the deprotection of self-assembled monolayers of alkylsilanes with photocleavable protecting groups and subsequent growth of nanostructured polymer brushes from these nanopatterned surfaces by atom-transfer radical polymerization.

Photolithographic techniques have been used to fabricate polymer brush micro- and nanostructures. On exposure to UV light with a wavelength of 244 nm, halogens were selectively removed from films of chloromethylphenyltrichlorosilane and 3-(2-bromoisobutyramido)propyl-triethoxysilane on silicon dioxide. Patterning was achieved at the micrometer scale, by using a mask in conjunction with the incident laser beam, and at the nanometer scale, by utilizing interferometric lithography (IL). Friction force microscopy images of patterned surfaces exhibited frictional contrast due to removal of the halogen but no topographical contrast. In both cases the halogenated surface was used as an initiator for surface atom-transfer radical polymerization. Patterning of the surface by UV lithography enabled the definition of patterns of initiator from which micro- and nanostructured poly[oligo(ethylene glycol)methacrylate] bottle brushes were grown. Micropatterned brushes formed on both surfaces exhibited excellent resistance to protein adsorption, enabling the formation of protein patterns. Using IL, brush structures were formed that covered macroscopic areas (approximately 0.5 cm²) but exhibited a full width at half maximum height as small as 78 nm, with a period of 225 nm. Spatially selective photolytic removal of halogens that are immobilized on a surface thus appears to be a simple, rapid, and versatile method for the formation of micro- and nanostructured polymer brushes and for the control of protein adsorption.

An approach to the integration of nanolithography with synthetic chemical methodology is described, in which near-field optical techniques are used to selectively deprotect films formed by the adsorption of aminosilanes protected by modified 2-nitrophenylethoxycarbonyl (NPEOC) groups. The NPEOC groups are functionalized at the m- or p-position with either a tetraethyleneglycol or a heptaethylene glycol adduct. We describe the synthesis of these bioresistant aminosilanes and the characterization of the resulting photoreactive films. Photodeprotection by exposure to UV light (λ = 325 nm) yielded the amine with high efficiency, at a similar rate for all four adsorbates, and was complete after an exposure of 2.24 J cm(-2). Following photodeprotection, derivatization by trifluoroacetic anhydride was carried out with high efficiency. Micropatterned samples, formed using a mask, were derivatized with aldehyde-functionalized polymer nanoparticles and, following derivatization with biotin, were used to form patterns of avidin-coated polymer particles. Fluorescence microscopy and atomic force microscopy data demonstrated that the intact protecting groups conferred excellent resistance to nonspecific adsorption. Nanometer-scale patterns were created using scanning near-field photolithography and were derivatized with biotin. Subsequent conjugation with avidin-functionalized polymer nanoparticles yielded clear fluorescence images that indicated dense attachment to the nanostructures and excellent protein resistance on the surrounding surface. These simple photocleavable protecting group strategies, combined with the use of near-field exposure, offer excellent prospects for the control of surface reactivity at nanometer resolution in biological systems and offer promise for integrating the top-down and bottom-up molecular fabrication paradigms.

The “Millipede”, developed by Binnig and co-workers (Bining, G. K.; et al. IBM J. Res. Devel. 2000, 44, 323.), elegantly solves the problem of the serial nature of scanning probe lithography processes, by deploying massive parallelism. Here we fuse the “Millipede” concept with scanning near-field photolithography to yield a “Snomipede” that is capable of executing parallel chemical transformations at high resolution over macroscopic areas. Our prototype has sixteen probes that are separately controllable using a methodology that is, in principle, scalable to much larger arrays. Light beams generated by a spatial modulator or a zone plate array are coupled to arrays of cantilever probes with hollow, pyramidal tips. We demonstrate selective photodeprotection of nitrophenylpropyloxycarbonyl-protected aminosiloxane monolayers on silicon dioxide and subsequent growth of nanostructured polymer brushes by atom-transfer radical polymerization, and the fabrication of 70 nm structures in photoresist by a Snomipede probe array immersed under water. Such approaches offer a powerful means of integrating the top-down and bottom-up fabrication paradigms, facilitating the reactive processing of materials at nanometer resolution over macroscopic areas.

The UV photodegradation of protein-resistant poly(oligo(ethylene glycol) methacrylate) (POEGMA) bottle-brush films, grown on silicon oxide by surface-initiated atom radical transfer polymerization, was studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Exposure to light with a wavelength of 244 nm caused a loss of polyether units from the brush structure and the creation of aldehyde groups that could be derivatized with amines. An increase was measured in the coefficient of friction of the photodegraded polymer brush compared to the native brush, attributed to the creation of a heterogeneous surface film, leading to increased energy dissipation through film deformation and the creation of new polar functional groups at the surface. Exposure of the films through a photomask yielded sharp, well-defined patterns. Analysis of topographical images showed that physical removal of material occurred during exposure, at a rate of 1.35 nm J(-1) cm(2). Using fluorescence microscopy, the adsorption of labeled proteins onto the exposed surfaces was studied. It was found that protein strongly adsorbed to exposed areas, while the masked regions retained their protein resistance. Exposure of the film to UV light from a scanning near-field optical microscope yielded submicrometer-scale patterns. These data indicate that a simple, rapid, one-step photoconversion of the poly(OEGMA) brush occurs that transforms it from a highly protein-resistant material to one that adsorbs protein and can covalently bind amine-containing molecules and that this photoconversion can be spatially addressed with high spatial resolution.

A common problem in applying biosensors for the detection of genomic DNA is detecting short sequences in large amounts of long double stranded DNA. A gold electrode modified with a conductive nanocomposite, poly(3,4-ethylene-dioxythiophene), and gold nanoparticles was functionalized with 2,6-Pyridinedicarboxylic acid. Immobilization of a 20-mer DNA probe as the bioreceptor was successfully carried out via a peptide bond on the surface of the modified electrode. Two segments of 15 and 20 base probes were designed and named as Capture and Reporter probes respectively. The 20-mer Reporter probe was complementary to the bioreceptor and the 15-mer Capture probe was designed to bind on to the surface of the iron oxide magnetic nanoparticles. A 35-base Target DNA complementary to the Capture and the Reporter probes was used as Template in the ligation process, with the ligation between the Reporter and Capture probes mediated by T4 ligase. Iron oxide magnetic nanoparticles functionalized with carboxylic groups on their surface synthesized in a new method were attached to the 15-mer Capture probe. After the denaturation of the final ligation product, the separation of the attached probes was carried out using 5 G permanent magnets in a three step washing procedure in TE buffer. The hybridization of the DNA bioreceptor and the Reporter probe attached to the Capture probe-Fe3O4 was monitored via oxidation and reduction of the new redox marker (ruthenium complex) intercalated into the double helix. This technique was found to be reliably repeatable. The indirect detection of genomic DNA using this method is significantly improved and showed high efficiency in small amounts of samples with the detection limit of 5.37 × 10−14 M.