Towards outperforming conventional sensor arrays with fabricated individual photonic vapour sensors inspired by Morpho butterflies.

Combining vapour sensors into arrays is an accepted compromise to mitigate poor selectivity of conventional sensors. Here we show individual nanofabricated sensors that not only selectively detect separate vapours in pristine conditions but also quantify these vapours in mixtures, and when blended with a variable moisture background. Our sensor design is inspired by the iridescent nanostructure and gradient surface chemistry of Morpho butterflies and involves physical and chemical design criteria. The physical design involves optical interference and diffraction on the fabricated periodic nanostructures and uses optical loss in the nanostructure to enhance the spectral diversity of reflectance. The chemical design uses spatially controlled nanostructure functionalization. Thus, while quantitation of analytes in the presence of variable backgrounds is challenging for most sensor arrays, we achieve this goal using individual multivariable sensors. These colorimetric sensors can be tuned for numerous vapour sensing scenarios in confined areas or as individual nodes for distributed monitoring.

Measuring atomic emission from beacons for long-distance chemical signaling.

In an effort to exploit chemistry for information science, we have constructed a system to send a message powered by a combustion reaction. Our system uses the thermal excitation of alkali metals to transmit an encoded signal over long distances. A message is transmitted by burning a methanol-soaked cotton string embedded with combinations of high, low, or zero levels of potassium, rubidium, and/or cesium ions. By measuring the intensities at the characteristic emission wavelengths of each metal in the near-infrared, 19 unique signals can be distinguished. We have built a custom telescope to detect these signals from 1 km away for nearly 10 min. The signal is isotropic, is self-powered, and has a low background. A potential application of this platform is for search and rescue signaling where another layer of information can be transmitted, in addition to the location of the beacon. This work, which seeks to encode and transmit information using chemistry instead of electronics, is part of the new field of "infochemistry".

Leveraging material properties in fluorescence anion sensor arrays: a general approach.

As the demand for probes suitable for sensor development increases, investigation of approaches that utilize known successful receptors gains in general importance. This study describes a two-prong approach that can be used as a guide to developing sensors from known receptors. First, the conversion of a simple receptor, calix[4]pyrrole, into a fluorescent probe to establish a ratiometric signal is described. Secondly, the sensors that employ an output from a single ratiometric calix[4]pyrrole probe are fabricated by using poly(ether-urethane) hydrogel copolymers. These hydrogels are designed to absorb, internalize and transport aqueous electrolytes. A sensor array of ten different poly(ether-urethane) matrices with varying comonomer proportions were doped with a single probe and were exposed to eight different anions: acetate, benzoate, fluoride, chloride, phosphate, pyrophosphate, hydrogen sulfide, and cyanide, eight urine samples and anti-inflammatory drugs (NSAIDs). The poly(ether-urethane) matrices comprise different proportions of anion-binding urethane moieties and different hydrophilicity given by the ratio between ethylene glycol ether and butylene glycol ether. This diversity in the hydration behavior provides different environment polarity, in which the recognition and self-assembly processes display enough diverse behavior to allow for unique response of the probe to the analytes. Furthermore, a single probe is shown to recognize eight different aqueous anions and eight urine samples when embedded in ten different polyurethanes in an array that displays 100 % classification accuracy. To demonstrate the potential of the concept for quantitative studies, an estimation of non-steroidal anti-inflammatory drugs ibuprofen and diclofenac in water and in saliva was performed. A limit of detection of 0.1 ppm and a dynamic range of 0.1-0.6 and 0.05-60 ppm was observed, respectively. Given the general difficulty of chemosensors to recognize aqueous anions, the fact that one probe recognizes eight different analytes attests to an enormous effect of the polymer environment on the recognition process. This method could be used to generate a variety of sensor arrays for various analyses including species that are difficult to recognize, such as small-molecule- and inorganic anions.

Assessing the stochastic intermittency of single quantum dot luminescence for robust quantification of biomolecules.

Single molecule detection schemes promise that one has the ability to reach the ultimate limit of detection: one molecule. In this paper, we use the stochastic luminescence of single semiconductor nanocrystals (quantum dots, QDs) to detect and localize particles as digital counts. These digital counts can be correlated to the concentration of analytes in solution. Here, we use total internal reflection fluorescence (TIRF) microscopy to probe individual QDs immobilized on a functionalized substrate. QDs have found their niche in the bioanalytical community due to their remarkable brightness and stability. Despite their numerous outstanding photophysical properties, QDs at the single particle level display a pronounced intermittent luminescence, posing a challenge for the detection of individual particles. In this paper, we demonstrate a reliable method for detecting QDs that takes advantage of these signal fluctuations by comparing the variations in the QD's fluorescence signals against variations of the background signal. The quantitative methodology developed here results in signal-to-background ratios up to 90:1, which is at least 8-times higher than the ratios obtained using methodologies relying solely on signal integration. This enhanced signal-to-background ratio facilitates a robust thresholding process and results in femtomolar limits of detection.

Dynamic microbead arrays for biosensing applications.

In this paper we present the development of an optical tweezers platform capable of creating on-demand dynamic microbead arrays for the multiplexed detection of biomolecules. We demonstrate the use of time-shared optical tweezers to dynamically assemble arrays of sensing microspheres, while simultaneously recording fluorescence signals in real time. The detection system is able to achieve multiplexing by using quantum dot nanocrystals as both signaling probes and encoding labels on the surface of the trapped microbeads. The encoding can be further extended by using a range of bead sizes. Finally, the platform is used to detect and identify three genes expressed by pathogenic strains of Escherichia coli O157:H7. The in situ actuation enabled by the optical tweezers, combined with multiplexed fluorescence detection offers a new tool, readily adaptable to biosensing applications in microfluidic devices, and could potentially enable the development of on-demand diagnostics platforms.

Iptycene-based fluorescent sensors for nitroaromatics and TNT.

Small-molecule fluorescent sensors (1-5) for the recognition of nitroaromatic compounds, such as 2,4-dinitrotoluene and the explosive TNT, were obtained by using a three-step dehydrohalogenation cycloaddition protocol. The interaction of the receptors and nitroaromatics was studied both in solution and in the solid state by using fluorescence spectroscopy and X-ray crystallography, respectively. It is shown that the iptycene receptors 1-5 provide a cavity suitable for binding nitroaromatic compounds in an edge-to-face mode, rather than simple ring-stacking interactions. The results obtained inspired us to develop an inexpensive, reliable and robust sensor for vapour detection of explosives. Polymer nanofibres are particularly suitable for the production of such TNT sensors as they accelerate the mass exchange between the polymer and the vapours of TNT. Quenching of the sensors took place within 1 min compared to 10 min for a glass-slide assay. Hence, the sensor performance can be improved by optimising the matrix material and morphology without resynthesising the sensor moieties.

InfoBiology by printed arrays of microorganism colonies for timed and on-demand release of messages.

This paper presents a proof-of-principle method, called InfoBiology, to write and encode data using arrays of genetically engineered strains of Escherichia coli with fluorescent proteins (FPs) as phenotypic markers. In InfoBiology, we encode, send, and release information using living organisms as carriers of data. Genetically engineered systems offer exquisite control of both genotype and phenotype. Living systems also offer the possibility for timed release of information as phenotypic features can take hours or days to develop. We use growth media and chemically induced gene expression as cipher keys or "biociphers" to develop encoded messages. The messages, called Steganography by Printed Arrays of Microbes (SPAM), consist of a matrix of spots generated by seven strains of E. coli, with each strain expressing a different FP. The coding scheme for these arrays relies on strings of paired, septenary digits, where each pair represents an alphanumeric character. In addition, the photophysical properties of the FPs offer another method for ciphering messages. Unique combinations of excited and emitted wavelengths generate distinct fluorescent patterns from the Steganography by Printed Arrays of Microbes (SPAM). This paper shows a new form of steganography based on information from engineered living systems. The combination of bio- and "photociphers" along with controlled timed-release exemplify the capabilities of InfoBiology, which could enable biometrics, communication through compromised channels, easy-to-read barcoding of biological products, or provide a deterrent to counterfeiting.

A practical approach to optical cross-reactive sensor arrays.

Supramolecular analytical chemistry has emerged as a new discipline at the interface of supramolecular and analytical chemistry. It focuses on analytical applications of molecular recognition and self-assembly. One of the important outcomes of the supramolecular analytical chemistry is the understanding of molecular aspects of sensor design, synthesis and binding studies of sensors while using rigorous methods of analytical chemistry as a touchstone to verify the viability of the supramolecular aspects of the sensor design. This critical review provides a simplified version of the chemometric procedures involved in realizing a successful analytical experiment that utilizes cross-reactive optical sensor arrays, and summarizes the current research in this field. This review also shows several examples of use of described chemometric methods for evaluation of chemosensors and sensor arrays. Thus, this review is aimed mostly at the readers who want to test their newly-developed chemosensors in cross-reactive arrays (169 references).

The power of the weak: recognition of ion pairs in water using a simple array sensor.

An array sensor comprising six off-the-shelf indicators doped in a poly(ether-urethane) recognizes five cations, seven anions and thirty-five ion pairs at pH 5-9 in water. Such a discrimination capacity and recognition efficiency (6 : 35) with > or = 93% accuracy is rare. Low cost and wide availability of various polymers and indicators could make this approach useful in numerous applications.

Ultrafast energy transfer in oligofluorene-aluminum bis(8-hydroxyquinoline)acetylacetone coordination polymers.

Understanding the excited-state dynamics in conjugated systems can lead to their better utilization in optical sensors, organic photovoltaics (OPVs), and organic light-emitting diodes (OLEDs). We present the synthesis of self-assembled coordination polymers comprising two types of fluorescent moieties: discrete fluorene oligomers of a well-defined length (n = 1-9) connected via aluminum(III) bis(8-quinolinolate)acetylacetone joints. Due to their well-defined structure, these materials allowed for a detailed study of energy migration processes within the materials. Thus, femtosecond transient spectroscopy was used to study the ultrafast energy transfer from the oligofluorene to the quinolinolate moieties, which was found to proceed at a rate of 10(11) s(-1). The experimental results were found to be in agreement with the behavior predicted according to the Beljonne's improved Forster model of energy transfer. In addition, the solid-state and semiconductor properties of these coordination polymers allowed for the fabrication of OLEDs. Preliminary experiments with simple two- and three-layer devices fabricated by spin-coating yield bright yellow electroluminescence with maximum brightness of 6000 cd/m(2), with a turn-on voltage of approximately 6 V and a maximum external quantum efficiency of up to 1.2%, suggesting their potential for use in PLED applications.

Polymer nanofibre junctions of attolitre volume serve as zeptomole-scale chemical reactors.

Methods allowing chemical reactions to be carried out on ultra-small scales in a controllable fashion are potentially important for a number of disciplines, including molecular electronics, photonics and molecular biology, and may provide fundamental insight into chemistry in confined spaces. Ultra-small-scale reactions also circumvent potential problems associated with reagent and product toxicity, and reduce energy consumption and waste generation. Here, we report a technique for performing chemical reactions on a zeptomole (10(-21) mol) scale. We show that electrospun polymer nanofibres with a diameter of 100-300 nm can be loaded with reactants, and that the junctions formed between crossed nanofibres can function as attolitre-volume reactors. Exposure to heat or solvent vapours fuses the fibres and initiates the reaction. The reaction products can be analysed directly within the nanofibre junctions by fluorescence measurements and mass spectrometry, and solvent extraction of multiple reactors allows product identification by common micromethods such as high-performance liquid chromatography-mass spectrometry.

Fluorescence sensor array for metal ion detection based on various coordination chemistries: general performance and potential application.

A sensor array containing 9 cross-reactive sensing fluorescent elements with different affinity and selectivity to 10 metal cations (Ca(2+), Mg(2+), Cd(2+), Hg(2+), Co(2+), Zn(2+), Cu(2+), Ni(2+), Al(3+), Ga(3+)) is described. The discriminatory capacity of the array was tested at different ranges of pH and at different cation concentrations using linear discriminant analysis (LDA). Qualitative identification of cations can be determined with over 96% of accuracy in a concentration range covering 3 orders of a magnitude (5-5000 microM). Quantitative analysis can be achieved with over 90% accuracy in the concentration range between 10 and 5000 microM. The array performance was also tested in identification of nine different mineral water brands utilizing their various electrolyte compositions and their Ca(2+), Mg(2+), and Zn(2+) levels. LDA cross-validation routine shows 100% correct classification for all trials. Preliminary results suggest that similar arrays could be used in testing of the consistency of the purification and manufacturing process of purified and mineral waters.

Harnessing a ratiometric fluorescence output from a sensor array.

Ratiometric fluorescence-based sensors are widely sought after because they can effectively convert even relatively small changes in optical output into a strong and easy-to-read signal. However, ratiometric sensor molecules are usually difficult to make. We present a proof-of-principle experiment that shows that efficient ratiometric sensing may be achieved by an array of two chromophores, one providing an on-to-off response and the second yielding an off-to-on response in a complementary fashion. In the case that both chromophores emit light of different color, the result is a switching of colors that may be utilized in the same way as from a true ratiometric probe. The chromophore array comprises two sensor elements: i) a polyurethane membrane with embedded N-anthracen-9-yl-methyl-N-7-nitrobenzoxa-[1,2,5]diazo-4-yl-N',N'-dimethylethylenediamine hydrochloride and ii) a membrane with N,N-dimethyl-N'-(9-methylanthracenyl)ethylenediamine. A combination of photoinduced electron transfer (PET) and fluorescence resonance energy transfer (FRET) allows for green-to-blue emission switching in the presence of Zn(II) ions. The sensing experiments carried out with different Zn(II) salts at controlled pH revealed that the degree of color switching in the individual sensor elements depends on both the presence of Zn(II) ions and the counter anion. These results suggest that sensing of both cations and anions may perhaps be extended to different cation-anion pairs.

Rational design of a minimal size sensor array for metal ion detection.

The focus of this study was to demonstrate that, in the luminescent sensors, the signal transduction may possibly be the most important part in the sensing process. Rational design of fluorescent sensor arrays for cations utilizing extended conjugated chromophores attached to 8-hydroxyquinoline is reported. All of the optical sensors utilized in the arrays comprise the same 8-hydroxyquinoline (8-HQ) receptor and various conjugated chromophores to yield a different response to various metal cations. This is because the conjugated chromophores attached to the receptor are partially quenched in their resting state, and upon the cation coordination by the 8-HQ, the resulting metalloquinolinolate complex displays a change in fluorescence. A delicate balance of conjugation, fluorescence enhancement, energy transfer, and a heavy metal quenching effect results in a fingerprint-like pattern of responses for each sensor-cation complex. Principal component analysis (PCA) and linear discriminant analysis (LDA) are used to demonstrate the contribution of individual sensors within the array, information that may be used to design sensor arrays with the smallest number of sensor elements. This approach allows discriminating between 10 cations by as few as two or even one sensor element. Examples of arrays comprising various numbers of sensor elements and their utility in qualitative identification of Ca(2+), Mg(2+), Cd(2+), Hg(2+), Co(2+), Zn(2+), Cu(2+), Ni(2+), Al(3+), and Ga(3+) ions are presented. A two-member array was found to identify 11 analytes with 100% accuracy. Also the best two of the sensors were tested alone and both were found to be able to discriminate among the samples with 99% and 96% accuracy, respectively. To illustrate the utility of this approach to a real-world application, identification of enhanced soft drinks based on their Ca(2+), Mg(2+), and Zn(2+) cation content was performed. The same approach to reducing array elements was used to construct three- and two-member arrays capable of identifying these complex analytes with 100% accuracy.

Simple molecule-based fluorescent sensors for vapor detection of TNT.

1,4-Diarylpentiptycenes (1a-e) were synthesized from 1,4-dichloro- or 1,4-difluoro-2,5-diarylbenzene derivatives by double base-promoted dehydrohalogenation to give corresponding arynes, which in the presence of anthracene undergo cycloaddition providing 1,4-diarylpentiptycenes in moderate overall yields. The resulting 1,4-diarylpentiptycenes show fluorescence modulated by the 1,4-aryl residues. The fluorescence is quenched in the presence of vapors of nitroaromatic compounds suggesting potential application in sensing of explosives.

Hydroxyquinolines with extended fluorophores: arrays for turn-on and ratiometric sensing of cations.

8-Hydroxyquinoline-based ligands with extended conjugated fluorophores were designed to provide turn-on and ratiometric signal output optimized for use in fluorescence-based sensor arrays, where the changes in blue and green channels of the RGB signal are used to distinguish between cationic analytes.

Supramolecular chemistry approach to the design of a high-resolution sensor array for multianion detection in water.

Reliable sensing of structurally similar anions in water is a difficult problem, and analytical tests and sensor devices for reliable sensing of multiple anions are very rare. This study describes a method for fabrication of simple colorimetric array-based assays for aqueous anion solutions, including complex analytes encountered in real-life applications. On the fundamental level, this method shows how the discriminatory capacity of sensor arrays utilizing pattern recognition operating in multianalyte environments may be dramatically improved by employing two key features. The synergy between the sensor and hydrogel host resembles the cooperative effects of an apoenzyme and cofactor: the host hydrogel helps extract the target anions from the bulk analyte while stripping the solvate molecules off the anions. In addition, the supramolecular studies of the affinity and selectivity of the potential sensors for target analytes allow for constructing an array predesigned for a particular analyte. To illustrate both aspects, an eight-sensor array utilizing colorimetric sensor materials showing selectivity for fluoride and pyrophosphate while displaying significant cross-reactivity for other anions such as carboxylates, phosphate, or chloride was used to differentiate between 10 anions. The quantitative analyses were also performed to show that the eight-sensor array was found to operate across 4 orders of magnitude concentrations (0.20-360 ppm; 10 microM to 20 mM). The applicability of this approach was demonstrated by analyzing several toothpaste brands. The toothpastes are complex analytes comprising both known and unknown anions in various concentrations. The fluoride-selective yet cross-reactive array is shown to utilize the fluoride content as the main differentiating factor while using the remaining anionic components for further differentiation between toothpaste brands.

Synthesis, structure, anion binding, and sensing by calix[4]pyrrole isomers.

The synthesis, structure, and anion binding properties of chromogenic octamethylcalix[4]pyrroles (OMCPs) and their N-confused octamethylcalix[4]pyrrole isomers (NC-OMCPs) containing an inverted pyrrole ring connected via alpha'- and beta-positions are described. X-ray diffraction analyses proved the structures of two synthesized isomeric pairs of OMCPs and NC-OMCPs. The addition of anions to solutions of chromogenic OMCPs and NC-OMCPs resulted in different colors suggesting different anion-binding behaviors. The chromogenic NC-OMCPs showed significantly stronger anion-induced color changes compared to the corresponding chromogenic OMCP, and the absorption spectroscopy titrations indicated that chromogenic OMCPs and NC-OMCPs also possess different anion binding selectivity. Detailed NMR studies revealed that this rather unusual feature stems from a different anion-binding mode in OMCPs and NC-OMCPs, one where the beta-pyrrole C-H of the inverted pyrrole moiety participates in the hydrogen-bonded anion-NC-OMCP complex. Preliminary colorimetric microassays using synthesized chromogenic calixpyrroles embedded in partially hydrophilic polyurethane matrices allow for observation of analyte-specific changes in color when the anions are administered in the form of their aqueous solutions and in the presence of weakly competing anions.