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Fluorescence based sensing is a versatile approach for the trace analysis outside of the laboratory, requiring suitable sensor materials and their integration into sensing devices. The versatility of fluorophores as probes, especially in terms of the possibility to tailor their optical as well as their recognition properties by synthetic modifications in a wide range, renders them a superior active component for the preparation of optical sensor devices. Recent works at BAM in this field include, for example, the detection of nerve gas agents, illustrating impressively the aforementioned benefits of fluorophores in optical sensing applications.
In the interdisciplinary approach presented here, we target hazardous gases such as ammonia, benzene, and hydrogen sulfide, next to others, which pose a major threat to human health and environmental safety and for which the availability of a sensitive and reliable detection method is highly desirable.
The dyes presented follow a “turn-on” fluorescence schematic which allows for the selective and sensitive detection of the respective gaseous analyte. The immobilization of the probe in polymeric matrices is then the next step toward the fabrication of a prototype device for molecular sensing.
There is an increasing interest in optical reporters like semiconductor and lanthanide-based nanocrystals with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, and safety barcodes. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as for upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation as well as by the lack of quantum yield standards with emission > 800 nm and especially > 1000 nm.
In this respect, we present the design of integrating sphere setups for absolute and excitation power densitydependent measurements of emission spectra and quantum yields in the wavelength region of 650 to 1650 nm
including calibration strategies and first candidates for potential fluorescence standards. Subsequently, the photoluminescence properties of different types of nanocrystals are presented and discussed including absolute photoluminescence measurements of upconversion and down conversion emission in different solvents.
There is an increasing interest in molecular and nanoscale with emission > 800 nm and recently also > 1000 nm for bioanalysis, medical diagnostics, bioimaging, and safety barcodes. Mandatory for the comparison of different emitter classes and the rational design of the next generation of reporters for the short wavelength infrared (SWIR) Region are reliable and quantitative photoluminescence measurements in this challenging wavelength region. This is of special relevance for nanocrystalline emitters like semiconductor quantum dots and rods as well as lanthanide-based upconversion and downconversion nanocrystals, where surface states and the accessibility of emissive states by quenchers largely control accomplishable photoluminescence quantum yields and hence, signal sizes and detection sensitivities from the reporter side. Such measurements are currently hampered by the lack of suitable methods and standards for instrument calibration and validation and quantum yield standards with emission > 800 nm and especially > 1000 nm.
In this respect, we present the design of integrating sphere setups for absolute and excitation power density-dependent measurements of emission spectra and photoluminescence quantum yields in the wavelength Region of 650 to 1650 nm including calibration strategies and first candidates for potential fluorescence standards.
Subsequently, the photoluminescence properties of different types of nanocrystals are presented including the upconversion and downconversion emission of differently sized and surface functionalized lanthanide-doped nanoparticles and photoluminescence quenching effects are quantified.
Upconversion nanoparticles (UCNPs) offer new strategies for luminescence-based sensing and imaging. One of the best studied materials are ..-NaYF4 UCNPs doped with 20 % Yb3+ and 2 % Er3+, which efficiently convert 976 nm light to photons emitted at 540 nm, 655 nm, and 845 nm, respectively, reveal long luminescence lifetimes (> 100 µs), are photostable and chemically inert. Their upconversion (UC) luminescence (UCL) properties are, however, strongly influenced by particle size, surface chemistry, and microenvironment. In addition, the multiphotonic absorption processes responsible for UCL render UCL excitation power density (..) dependent. This makes quantitative UCL measurements as well as the determination of UC quantum yields (.UC) very challenging.
The rational design of brighter UCNPs particle architectures and the interest in identifying optimum particle architectures for FRET-based sensing and imaging schemes, which often rely on core-only UCNPs to minimize donor-acceptor distances, encouraged us to assess the influence of particle size and P on UCL. Here, we present the photophysical properties of a series of hexagonal NaYF4 UCNPs with sizes from 10 to 43 nm with different surface ligands dispersed in organic solvents and water studied by steady state and time-resolved fluorometry as well as quantitatively by integrating sphere spectrometry with P varied over about three orders of magnitude. Our results underline the need for really quantitative luminescence studies for mechanistic insights and the potential of high P to compensate for UCL quenching due to high energy phonons and surface effects.
Comparison of fluorescence measurements performed on different fluorescence instruments, analyte quantification from fluorescence intensities as well as the determination of fluorescence quantum yields require instrument calibration and consideration of the wavelength-dependent instrument-specific quantities spectral photon flux reaching the sample and spectral responsivity. Here, we present guidelines and recommendations for the qualification of fluorescence instruments and introduce suitable chromophore-based reference materials. Moreover, the design concepts of the different BAM fluorescence standards are discussed.
Ammonia and its reaction products can cause considerable damage of human health and ecosystems, increasing the necessity for reliable and reversible sensors to monitor traces of gaseous ammonia in ambient air directly on-site or in the field. Although various types of gas sensors are available, fluorescence sensors have gained importance due to advantages such as high sensitivity and facile miniaturization.
Here, we present the development of a sensor material for the detection of gaseous ammonia in the lower ppm to ppb range by incorporation of a fluorescent dye, which shows reversible fluorescence modulations as a function of analyte concentration, into a polymer matrix to ensure the accumulation of ammonia. A gas standard generator producing standard gas mixtures, which comply with the metrological traceability in the desired environmentally relevant measurement range, was used to calibrate the optical sensor system. To integrate the sensor material into a mobile device, a prototype of a hand-held instrument was developed, enabling straightforward data acquisition over a long period.
Semiconductor nanocrystals with a spherical (QDs) core and a spherical or a rod-shaped Shell, u.a., so-called Quantum dot-Quantum rods (QDQRs) are increasingly used as fluorescent Reporters or optically active components in the life and material science, e.g., in solid state lightening including Plasma Displays. (1,2) Morever, there is an increasing interest in materials with emission >800 nm for bioanalysis, medical diagnostics, and safety barcodes. Prerequisites for the mechanistic understanding of nonradiativ decay channels needed for the rational design of improved nanomaterials and the comparison of material Performance are reliable fluorescence measurements and validated methods for the assessment of their surface chemistry. (3,4) The latter is of particular importance for nanocrystalline Emitters, where surface states and the accessibility of emissive states by quenchers largely control photoluminescence properties. (5) Here, we present results from systematic spectroscopic studies including absolutely measured photolumunescence Quantum yields of different vissible and NIR emisisve QD and QDQRs Systems of varying particle architecture size and surface chemistries in Dispersion and embedded in salt crystals. (6,7)
The fluorescence properties of three molecular rotors, related to 4-dimethylamino-4-nitrostilbene (4-DNS), are studied versus different diesel/kerosene blends. In nonviscous solvents, these compounds can populate a twisted intramolecular charge transfer state which deactivates nonradiatively, successfully suppressing fluorescence emission. Solution experiments with diesel/kerosene blends showed a good linear correlation between the fluorescence intensity of the probe molecules and the diesel fraction of the blend. The dyes have been immobilized on paper, retaining their fluorescence behavior, i.e., negligible emission in the presence of nonviscous organic solvents and increasing fluorescence when the environment is increasingly viscous. When the impregnated paper is devised as a test strip, the latter is compatible with a newly designed smartphone reader system, which allows in-the-field measurements. The method can safely detect the presence of kerosene in diesel at ≥7%, which competes favorably with current standard methods for the detection of diesel adulteration.
A 2,3-diaminophenazine bis-urea fluorescent probe monomer (1) was developed. It responds to phenylphosphate and phosphorylated amino acids in a ratiometric fashion with enhanced fluorescence accompanied by the development of a redshifted emission band arising from an excited-state proton transfer (ESPT) process in the hydrogen-bonded probe/analyte complex. The two urea groups of 1 form a cleft-like binding pocket (Kb>10^10 L^2 mol^-2 for 1:2 complex). Imprinting of 1 in presence of ethyl ester- and fluorenylmethyloxycarbonyl (Fmoc)-protected phosphorylated tyrosine (Fmoc-pTyr-OEt) as the template, methacrylamide as co-monomer, and ethyleneglycol dimethacrylate as crosslinker gave few-nanometer-thick molecularly imprinted polymer (MIP) shells on silica core microparticles with excellent selectivity for the template in a buffered biphasic assay. The supramolecular recognition Features were established by spectroscopic and NMR studies. Rational screening of comonomers and cross-linkers allowed to single out the best performing MIP components, giving significant imprinting factors (IF>3.5) while retaining ESPT emission and the ratiometric response in the thin polymer shell. Combination of the bead-based detection scheme with the phase-transfer assay dramatically improved the IF to 15.9, allowing sensitive determination of the analyte directly in aqueous media.
In this review we present new concepts and recent progress in the application of semiconductur quantum dots (QD) as labels in two important areas of biology, bioimaging and biosensing. We analyze the biologically relevant properties of QDs focusing on the following topics: QD surface treatment and stability labeling of cellular structures and receptors with QDs, incorporation of QDs in living cells, cytotoxicity of QDs and influence of the biolocical environment on the biological and optical properties of QDs. Initially, we consider utilization of QDs as agants in high-resolution bioimaging techniques that can provide information at the molecular levels. The deverse range of modern live-cell QD-based imaging techniques with resolution far beyond the diffraction limit of light is examined. In each technique, we discuss the pros and cons of QD use and deliberate how QDs can be further engineered to facilitate their application in the respective imaging techniques and to produce significant improvements in resolution. Then we review QD-based point-of-care bioassays, bioprobes, and biosensors designed in different formats ranging from analytic biochemistry assays and ELISA, to novel point-of-care smartphone integrated QD-based biotests. Here, a wide range of QD-based fluorescence bioassays with optical transduction, electrochemiluminescence and photoelectrochemical assays are discussedc. Finally, this review provides an analysis of the prospects of application of QDs in selected important Areas of biology.