The use of a novel smartphone testing platform for the development of colorimetric sensor receptors for food spoilage.

This work presents a novel smartphone testing platform for the validation of colorimetric sensor receptors (CSRs) in the form of layers that enables reliable and straightforward determination of their color change in a closed system using a commercially available color sensor. The food-compatible model CSR used for the method development was made of black carrot extract and ethyl cellulose. The colorimetric responses were studied in detail for NH3, dimethylamine (DMA), and trimethylamine (TMA) by analyzing changes in the value of the total color difference (ΔE) with the increasing logarithm of the mass concentration (log γ) of the analytes. The method was partially validated for the detection limit (LOD), the limit of quantification, sensitivity, and linear γ range. The fastest reaction times were obtained for the NH3 analyte, while the calculated LOD values were quite similar (1.48 mg L-1 for NH3, 1.55 mg L-1 for DMA, and 1.58 mg L-1 for TMA). The applicability of CSRs was shown for different types of muscle food. Frozen (boneless and skinless) hake fillets were used for additional experimental work in which the color changes of the CSRs were correlated with the values of the total volatile basic nitrogen (TVB-N) and the total counts of aerobic and anaerobic microorganisms. The developed testing platform shows great promise for the development of CSRs that define the quality of a broad variety of muscle food.

Naphthalimide-Piperazine Derivatives as Multifunctional "On" and "Off" Fluorescent Switches for pH, Hg2+ and Cu2+ Ions.

Novel 1,8-naphthalimide-based fluorescent probes NI-1 and NI-2 were designed and screened for use as chemosensors for detection of heavy metal ions. Two moieties, methylpyridine (NI-1) and hydroxyphenyl (NI-2), were attached via piperazine at the C-4 position of the napthalimide core resulting in a notable effect on their spectroscopic properties. NI-1 and NI-2 are pH sensitive and show an increase in fluorescence intensity at around 525 nm (switch "on") in the acidic environment, with pKa values at 4.98 and 2.91, respectively. Amongst heavy metal ions only Cu2+ and Hg2+ had a significant effect on the spectroscopic properties. The fluorescence of NI-1 is quenched in the presence of either Cu2+ or Hg2+ which is attributed to the formation of 1:1 metal-ligand complexes with binding constants of 3.6 × 105 and 3.9 × 104, respectively. The NI-1 chemosensor can be used for the quantification of Cu2+ ions in sub-micromolar quantities, with a linear range from 250 nM to 4.0 µM and a detection limit of 1.5 × 10-8 M. The linear range for the determination of Hg2+ is from 2 µM to 10 µM, with a detection limit of 8.8 × 10-8 M. Conversely, NI-2 behaves like a typical photoinduced electron transfer (PET) sensor for Hg2+ ions. Here, the formation of a complex with Hg2+ (binding constant 8.3 × 103) turns the green fluorescence of NI-2 into the "on" state. NI-2 showed remarkable selectivity towards Hg2+ ions, allowing for determination of Hg2+ concentration over a linear range of 1.3 µM to 25 µM and a limit of detection of 4.1 × 10-7 M.

Indicator Layers Based on Ethylene-Vinyl Acetate Copolymer (EVA) and Dicyanovinyl Azobenzene Dyes for Fast and Selective Evaluation of Vaporous Biogenic Amines.

The article presents naked-eye methods for fast, sensitive, and selective detection of isopentylamine and cadaverine vapours based on 4-N,N-dioctylamino-4'-dicyanovinylazobenzene (CR-528) and 4-N,N-dioctylamino-2'-nitro-4'-dicyanovinylazobenzene (CR-555) dyes immobilized in ethylene-vinyl acetate copolymer (EVA). The reaction of CR-528/EVA and CR-555/EVA indicator layers with isopentylamine vapours caused a vivid colour change from pink/purple to yellow/orange-yellow. Additionally, CR-555/EVA showed colour changes upon exposure to cadaverine. The colour changes were analysed by ultraviolet⁻visible (UV/VIS) molecular absorption spectroscopy for amine quantification, and the method was partially validated for the detection limit, sensitivity, and linear concentration range. The lowest detection limits were reached with CR-555/EVA indicator layers (0.41 ppm for isopentylamine and 1.80 ppm for cadaverine). The indicator layers based on EVA and dicyanovinyl azobenzene dyes complement the existing library of colorimetric probes for the detection of biogenic amines and show great potential for food quality control.

Design and Characterization of Dicyanovinyl Reactive Dyes for the Colorimetric Detection of Thiols and Biogenic Amines.

The synthesis of two new azobenzene dyes, namely CR-528 and CR-555, and their spectral properties in ethanol solution are described. The recognition of sulfur-containing analytes (2-mercaptoethanol (2-ME), sodium hydrosulfide (NaHS)), and biogenic amines (spermine, spermidine, ethanolamine) bestowed significant spectral changes with color changes from pink/purple to pale yellow/orange-yellow. The nitro acceptor group in the dicyanovinyl reactive dye contributes to higher sensitivity and lower detected analyte concentrations. The absorption maxima of both the dyes are at wavelengths compatible with low-cost light sources and detectors, making them excellent candidates for optical probes that are economic, simple to use, and do not require well-trained personnel.

The Development of Indicator Cotton Swabs for the Detection of pH in Wounds.

Indicator cotton swabs have been developed in order to enable faster, less expensive, and simpler information gathering of a wound status. Swabs are normally used for cleaning the wound, but here, they were covalently functionalized with indicator chemistry. Thus, they in principle enable simultaneous wound cleaning and wound pH detection. Using an indicator dye with a color change from yellow to red, combined with an inert dye of blue color, a traffic light color change from green to red is induced when pH increases. The indicator cotton swabs (ICSs) show a color change from green (appropriate wound pH) to red (elevated wound pH). This color change can be interpreted by the naked eye as well as by an optical color measurement device in order to obtain quantitative data based on the CIE L*a*b* color space. Two types of swabs have been developed-indicator cotton swabs ICS1 with a sensitive range from pH 5 to 7 and swabs ICS2 with a sensitive range from 6.5 to 8.5. The swabs are gamma-sterilized and the effect of sterilization on performance was found to be negligible. Furthermore, cytotoxicity testing shows cell viability and endotoxin levels to be within the allowable range.

Developing a sensor layer for the optical detection of amines during food spoilage.

A colourimetric sensor layer has been developed for ammonia and biogenic amines. Amine exposure induces a traffic light colour change from green to red. Recognition is performed by a pH indicator dye, covalently immobilised onto cellulose microparticles. The sensor microparticles are embedded into food-grade silicone. Selectivity of the pH indicator dye towards gaseous amine is obtained by complete embedding of the sensor particles within the ion-impermeable silicone. A response time of 1.5h has been achieved, with a reverse response occurring after 20h. This time frame is considered sufficient for spoilage processes. Cytotoxicity studies confirm the layers are non-toxic.

Mitoxantrone-loaded zeolite beta nanoparticles: preparation, physico-chemical characterization and biological evaluation.

This article describes the preparation and the physico-chemical characterization of a new host-guest system consisting of zeolite beta nanoparticles as host and mitoxantrone as guest. The resulting host-guest system mitoxantrone@beta is characterized in terms of morphology (transmission electron microscopy, dynamic light scattering), structure (powder wide-angle X-ray diffraction, nitrogen sorption), surface charge (ξ-potential measurements), and optical properties (UV-visible absorption, steady-state fluorescence). Mitoxantrone@beta particles are monodisperse in size with a mean diameter centered around 100 nm. Mitoxantrone guest molecules are adsorbed at the micropore entrances of zeolite host. Resulting nanoparticles retrieve the interesting optical properties of guest molecules with a fluorescence emission band in the near-infrared region. Mitoxantrone loading is comparatively evaluated by three different means (elemental analysis, direct and indirect UV-visible absorption studies) showing a loading level of 6.8 µmol/g. Mitoxantrone@beta nanoparticles also show a noticeable cytotoxic effect when applied to cancer cells.

Fluorescence dye as novel label molecule for quantitative SERS investigations of an antibiotic.

Within this contribution, the proof-of-principle for a new concept for indirect surface-enhanced Raman spectroscopy (SERS) detection is presented. The fluorescence dye FR-530 is applied as a label molecule for the antibiotic erythromycin. The antibiotic binds directly to the label molecule. Changes within the SERS spectrum of the fluorescence dye appearing with the presence of the antibiotic are utilized for the detection and quantitative investigations of erythromycin. With the new concept of binding the label molecule directly to the analyte molecule, the application of linkage compounds like antibodies or any other recognition molecules becomes dispensable.

Magnetic and fluorescent core-shell nanoparticles for ratiometric pH sensing.

This paper describes the preparation of nanoparticles composed of a magnetic core surrounded by two successive silica shells embedding two fluorophores, showing uniform nanoparticle size (50-60 nm in diameter) and shape, which allow ratiometric pH measurements in the pH range 5-8. Uncoated iron oxide magnetic nanoparticles (∼10 nm in diameter) were formed by the coprecipitation reaction of ferrous and ferric salts. Then, they were added to a water-in-oil microemulsion where the hydrophilic silica shells were obtained through hydrolysis and condensation of tetraethoxyorthosilicate together with the corresponding silylated dye derivatives-a sulforhodamine was embedded in the inner silica shell and used as the reference dye while a pH-sensitive fluorescein was incorporated in the outer shell as the pH indicator. The magnetic nanoparticles were characterized using vibrating sample magnetometry, dynamic light scattering, transmission electron microscopy, x-ray diffraction and Fourier transform infrared spectroscopy. The relationship between the analytical parameter, that is, the ratio of fluorescence between the sensing and reference dyes versus the pH was adjusted to a sigmoidal fit using a Boltzmann type equation giving an apparent pK(a) value of 6.8. The fluorescence intensity of the reference dye did not change significantly (∼3.0%) on modifying the pH of the nanoparticle dispersion. Finally, the proposed method was statistically validated against a reference procedure using samples of water and physiological buffer with 2% of horse serum, indicating that there are no significant statistical differences at a 95% confidence level.

Surface-functionalized fluorescent silica nanoparticles for the detection of ATP.

The design of two-dyed fluorescent silica nanoparticles for ATP detection is presented. The indicator dye possesses a dipicolyl-amine (DPA) unit complexed with Zn(II) as a receptor function for ATP while a rhodamine derivative is used as the reference dye. The nanoparticles were fully characterized regarding analytical performance, morphology and cytocompatibility.

Star-shaped tripodal chemosensors for the detection of aliphatic amines.

In this work, three new tripodal triphenylamine dyes are presented that are capable of reversibly binding amines and diamines to form hemiaminals through a covalent bond. The dyes were synthesized by the Heck reaction and possess stilbene units with one, two, or three trifluoroacetyl groups as receptor moieties. Their interaction with amines and diamines led to changes in their absorption and emission properties, which were detected by UV/Vis and fluorescence spectroscopy. The influence of the number of trifluoroacetyl receptor moieties on the selectivity and sensitivity of the dyes was studied. Enhanced sensitivity and selectivity for diaminoalkanes was found for the dye we have labeled Tripod-1, with three chemically reactive trifluoroacetyl groups, related to only one or two trifluoroacetyl groups in the dye molecule.

Molecular recognition of the antiretroviral drug abacavir: towards the development of a novel carbazole-based fluorosensor.

Due to their optical and electro-conductive attributes, carbazole derivatives are interesting materials for a large range of biosensor applications. In this study, we present the synthesis routes and fluorescence evaluation of newly designed carbazole fluorosensors that, by modification with uracil, have a special affinity for antiretroviral drugs via either Watson-Crick or Hoogsteen base pairing. To an N-octylcarbazole-uracil compound, four different groups were attached, namely thiophene, furane, ethylenedioxythiophene, and another uracil; yielding four different derivatives. Photophysical properties of these newly obtained derivatives are described, as are their interactions with the reverse transcriptase inhibitors such as abacavir, zidovudine, lamivudine and didanosine. The influence of each analyte on biosensor fluorescence was assessed on the basis of the Stern-Volmer equation and represented by Stern-Volmer constants. Consequently we have demonstrated that these structures based on carbazole, with a uracil group, may be successfully incorporated into alternative carbazole derivatives to form biosensors for the molecular recognition of antiretroviral drugs.

Spectroscopic Properties of Azobenzene-Based pH Indicator Dyes: A Quantum Chemical and Experimental Study.

The UV-visible absorption spectra of six new optical sensors based on acidochromic azobenzenes have been measured and assigned with the help of quantum chemical calculations. The investigated compounds are able to monitor the pH in the range from pH 3-10. Using the hybrid density functional PBE0 and including solvent effects with a polarized continuum model, the agreement between the experimental and theoretical UV/vis spectra of the dyes in their neutral and anionic forms is very good. The spectroscopic ππ* states, responsible for the optical properties of the sensors, are described within an accuracy of 0.1 eV. Similar accuracy is demonstrated in the nπ* states. The ππ* states can be assigned as a charge transfer from the aromatic π orbital localized in the azo-phenol moiety to the antibonding π* of the azo group. Under basic conditions, the spectrum is bathochromically shifted and more intense than in acid media. Upon substitution in the phenyl moiety, red- or blue-shifts of the UV-visible bands are observed depending on whether the substituent is electron-donor or -withdrawing, respectively. These effects are stronger at high pH values and can be rationalized in terms of the stabilization and/or destabilization of the involved frontier orbitals.

On the design of fluorescent ratiometric nanosensors.

Advances in nanoparticle technology have recently offered new tools to the bioanalytical field of research. In particular, new nanoparticle-based sensors have appeared able to give quantitative information about different species (ions, metabolites, biomolecules) in biosamples through ratiometric measurements. This article describes the methodologies developed so far in the design of such nanosensors. In particular, the different approaches to immobilize fluorescent chemosensor dyes to nanoparticles are presented. Concept designs of ratiometric nanosensors in terms of composition and architecture are also described and illustrated with examples taken from the literature.

On the application of different bimetallic alloy nanoparticle combinations in fiber optic surface plasmon resonance salinity sensor and its performance optimization against thermal effects.

In the present work, we have theoretically investigated the capability of the layer composed of various combinations of bimetallic alloy nanoparticles to be used in fiber optic salinity sensor based on the technique of surface plasmon resonance (SPR). The metals considered for the present analysis are silver, gold, copper, and aluminum. The performance of the sensor with six different bimetallic alloy nanoparticle combinations is evaluated and compared. Furthermore, the performance optimization is carried out in order to minimize the effect of the variation in operating temperature. The overall performance is analyzed in terms of four parameters: sensitivity, signal-to-noise ratio, detection limit, and operating range for the salinity detection in the water sample. On the basis of the comparisons and logistic criteria, the best possible bimetallic alloy combinations along with requisite alloy composition ratio are predicted. The nanoparticle layer made of bimetallic alloy is capable of simultaneously providing larger values of sensitivity, signal-to-noise ratio, detection and operating range, against the temperature-variation compared to single metallic nanoparticle layer.

An ATP fluorescent chemosensor based on a Zn(II)-complexed dipicolylamine receptor coupled with a naphthalimide chromophore.

A fluorescent naphthalimide chemosensor for ATP bearing a dipicolylamine group complexed with a Zn(II) metal as a receptor moiety was synthesized and its sensing properties regarding ATP and other related phosphate species were evaluated.

Ratiometric pH-nanosensors based on rhodamine-doped silica nanoparticles functionalized with a naphthalimide derivative.

This paper describes the preparation of two-dye-doped silica nanoparticles for ratiometric pH measurements in the biologically relevant pH-range. While a rhodamine derivative is embedded in a silica core and used as the reference, a pH-sensitive naphthalimide dye is immobilized on the previously amino-functionalized core through two different approaches. Either the naphthalimide's carboxylic group is activated to a succinimidyl-ester to form an amide bond or the system can be built up via solid-phase organic synthesis in only two steps. Both types of nanosensors are characterized in terms of morphology (dynamic light scattering, transmission electron microscopy) and optical properties (steady-state fluorescence spectroscopy). In terms of application, e.g. reproducibility and handling of the synthesis, the first approach gave very good results with respect to size and size distribution and a pK(a) value of 6.55 was found that is comparable to the free indicator dye in solution. The solid-phase organic synthesis method proves the possibility of covalent immobilization of naphthalimides to amino-functionalized surfaces, showing the stability of the polymeric substrate and achieving comparable results for pH sensing.

Fluorescent polyacrylamide nanoparticles for naproxen recognition.

We present the synthesis of fluorescent acrylamide nanoparticles (FANs) capable of recognizing non-steroidal anti-inflammatory drugs (NSAIDs) in buffered aqueous solutions. Within this important group, we selected naproxen, one of the 2-arylpropionic acids (profens), due to its use for the treatment of moderate pain, fever, and inflammation. The nanosensors were prepared under mild conditions of inverse microemulsion polymerization using aqueous acrylamide as the monomer and N,N'-methylenebisacrylamide as the cross-linker, employing the surfactants polyoxyethylene-4-lauryl ether (Brij 30) and sodium bis(2-ethylhexyl)sulfosuccinate in hexane. Furthermore, a fluorescent monomer, (E)-4-[4-(dimethylamino)styryl]-1-[4-(methacryloyloxymethyl)benzyl]pyridinium chloride (mDMASP) has been synthesized and incorporated into the nanoparticles. The nanosensors exhibit a broad absorbance at around 460 nm and a structureless fluorescence band with maximum at 590 nm in 0.5 M phosphate buffer (pH = 7.2). The recognition process is performed on the basis of ionic interactions which are monitored by the fluorescence increase at 590 nm upon addition of different concentrations of naproxen. The FANs show a size distribution in the range of 20-80 nm, with a hydrodynamic diameter of 34 nm. In order to assess the selectivity of the FANs, a systematic study was conducted on the effect produced by drugs and biomolecules that could interfere with the analysis of naproxen.

Evaluation of fluorescent polysaccharide nanoparticles for pH-sensing.

The comprehensive characterization of novel dextran nanoparticles with regard to their suitability as pH-sensors for analytical applications (e.g. in physiology) is described. The nanoparticles are labeled with both a pH-indicator dye (fluorescein isothiocyanate, FITC) and a reference dye (sulforhodamine B acid chloride) as an internal standard. The fluorescence intensity of FITC increases with increasing pH, whereas the signal of the reference dye remains constant. Plotting the ratio of both signals against the pH gives a pK(a) of 6.45, which is appropriate for most of the measurement purposes. Furthermore, the influence of temperature, ionic strength and oxidizing substances on the performance of the fluorophores inside the dextran nanoparticles is examined. These results are compared to the dissolved dyes in order to evaluate if the dextran matrix affects the fluorescence properties of the sensor and the reference dye, and whether or not these nanosensors are suitable for pH-sensing in biological samples.