Luminescent alloyed quantum dots for turn-off enzyme-based assay.

A new bioanalytical labeling system based on alloyed quantum dots' (QDs) photoluminescence quenching caused by an enzymatic reaction has been developed and tested for the first time. The catalytic role of the enzyme provides high sensitivity and the possibility of varying detecting time to improve assay sensitivity. Alloyed luminescent QDs were chosen in view of their small size (5-7 nm) and the high sensitivity of their optical properties to physicochemical interactions. Here, we described the synthesis of alloyed luminescent QDs and demonstrated the possibility of using them as a luminescent turn-off substrate for enzymatic assay. Synthesized alloyed QDs were found to be a sensitive turn-off substrate for glucose oxidase in homogeneous and heterogeneous assay models. CdZnSeS and CdZnSeS/ZnS QDs covered with dihydrolipoic acid and 2-mercaptoethanol were tested. A glucose oxidase limit of detection of 6.6 nM for the heterogenous high-throughput model assay was reached.

Magneto-Optical Stark Effect in Fe-Doped CdS Nanocrystals.

Fe2+ doping in II-VI semiconductors, due to the absence of energetically accessible multiple spin state configurations, has not given rise to interesting spintronic applications. In this work, we demonstrate for the first time that the interaction of homogeneously doped Fe2+ ions with the host CdS nanocrystal with no clustering is different for the two spin states and produces two magnetically inequivalent excitonic states upon optical perturbation. We combine ultrafast transient absorption spectroscopy and density functional theoretical analysis within the ground and excited states to demonstrate the presence of the magneto-optical Stark effect (MOSE). The energy gap between the spin states arising due to MOSE does not decay within the time frame of observation, unlike optical and electrical Stark shifts. This demonstration provides a stepping-stone for spin-dependent applications.

An engineered azurin with a lanthanide binding site capable of copper sensing.

Proteins with hetero-bimetallic metal centers can catalyze important reactions and are challenging to design. Azurin is a mononuclear copper center that has been extensively studied for electron transfer. Here we inserted the lanthanide binding tag (LBT), which binds lanthanide with sub µM affinity, into the copper binding loop of azurin, while keeping the type 1 copper center unperturbed. The resulting protein, Az-LBT, which has two metal bonding centers, shows strong luminescence upon coordination with Tb3+ and luminescence quenching upon Cu2+ binding. The in vitro luminescence quenching has high metal specificity and a limit-of-detection of 0.65 µM for Cu2+. With the low background from lanthanide's long luminescence lifetime, bacterial cells expressing Az-LBT in the periplasm also shows sensitivity for metal sensing.

A Eu(III)-based Metal Organic Framework: Selective Sensing of Picric Acid and Nursing Application Values On the Cerebral Edema Induced by Cerebral Hemorrhage Via Reducing the Coagulation Factor II Activity.

A new three-dimensional lanthanide metal-organic framework (Ln-MOF), [Eu4(L)4(H2O)8]·10H2O (1, H3L = biphenyl-3'-nitro-3,4',5-tricarboxylic acid), has been constructed via solvothermal technology and its framework has been detected by the single-crystal X-ray diffraction and elemental analyses. Complex 1 with typical emission of Eu3+ ion represents dramatic luminescence quenching affect for picric acid (PA) and the linear Stern-Volmer plot was surveyed in the consistence, ranging from 0.05 to 0.15 mM (Ksv = 98,074 M- 1). Its therapeutic effect of the compound on the cerebral edema caused by cerebral hemorrhage was estimated and the mechanism was explored. Possible binding interactions have been investigated by molecular docking simulations, from which the binding interactions are identified and the carboxyl oxygens are responsible for those identified interactions.

New method for calibrating optical dissolved oxygen sensors in seawater based on an intelligent learning algorithm.

Oxygen sensors based on luminescence quenching are the most commonly used instruments for in situ measurement in seawater due to their accuracy and long-term stability. The calibration method of the sensor is crucial for their accuracy. Conventional methods exhibit some defects, such as strict control of calibration conditions and cumbersome and time-consuming operation. To improve calibration operation and obtain good calibration results, a new calibration method was proposed for the optical dissolved oxygen sensor in seawater based on an intelligent learning algorithm. The sensor to be calibrated and the reference sensor were deployed in the water for synchronous measurements. The calibration system consisted of a temperature-regulated device and a sampling method to improve calibration operation. An intelligent learning algorithm was used to train the calibration data and model the oxygen response of the sensor. Calibration and test results in both laboratory and field showed that the new calibration method is feasible and efficient. It is highly significant for sensor development and in situ measurement in seawater.

Dual Oxygen and Temperature Luminescence Learning Sensor with Parallel Inference.

A well-known approach to the optical measure of oxygen is based on the quenching of luminescence by molecular oxygen. The main challenge for this measuring method is the determination of an accurate mathematical model for the sensor response. The reason is the dependence of the sensor signal from multiple parameters (like oxygen concentration and temperature), which are cross interfering in a sensor-specific way. The common solution is to measure the different parameters separately, for example, with different sensors. Then, an approximate model is developed where these effects are parametrized ad hoc. In this work, we describe a new approach for the development of a learning sensor with parallel inference that overcomes all these difficulties. With this approach we show how to generate automatically and autonomously a very large dataset of measurements and how to use it for the training of the proposed neural-network-based signal processing. Furthermore, we demonstrate how the sensor exploits the cross-sensitivity of multiple parameters to extract them from a single set of optical measurements without any a priori mathematical model with unprecedented accuracy. Finally, we propose a completely new metric to characterize the performance of neural-network-based sensors, the Error Limited Accuracy. In general, the methods described here are not limited to oxygen and temperature sensing. They can be similarly applied for the sensing with multiple luminophores, whenever the underlying mathematical model is not known or too complex.

Optical Oxygen Sensing with Artificial Intelligence.

Luminescence-based sensors for measuring oxygen concentration are widely used in both industry and research due to the practical advantages and sensitivity of this type of sensing. The measuring principle is the luminescence quenching by oxygen molecules, which results in a change of the luminescence decay time and intensity. In the classical approach, this change is related to an oxygen concentration using the Stern-Volmer equation. This equation, which in most cases is non-linear, is parameterized through device-specific constants. Therefore, to determine these parameters, every sensor needs to be precisely calibrated at one or more known concentrations. This study explored an entirely new artificial intelligence approach and demonstrated the feasibility of oxygen sensing through machine learning. The specifically developed neural network learns very efficiently to relate the input quantities to the oxygen concentration. The results show a mean deviation of the predicted from the measured concentration of 0.5% air, comparable to many commercial and low-cost sensors. Since the network was trained using synthetically generated data, the accuracy of the model predictions is limited by the ability of the generated data to describe the measured data, opening up future possibilities for significant improvement by using a large number of experimental measurements for training. The approach described in this work demonstrates the applicability of artificial intelligence to sensing technology and paves the road for the next generation of sensors.

Carbohydrates and Charges on Oligo(phenylenethynylenes): Towards the Design of Cancer Bullets.

Two new tetralkylammonium-OPEs, bearing one or two positively charged groups directly linked to the aromatic residues and two ß-d-glucopyranose terminations, were synthesized. Their peculiar structural features, joining the biologically relevant sugar moieties, flat aromatic cores and positive charges, make these luminescent dyes soluble in aqueous media and able to strongly interact with DNA. As a result of UV/Vis spectral variations, DNA melting temperature measures, viscometric titrations and induced CD, we propose a partial insertion of the OPEs aromatic core into the helix, stabilized by glucose H-bonding with the groups accessible from the grooves. This interaction leads to the quenching of the OPE luminescence due to guanine reduction. The biocompatibility of the monocationic OPE with healthy and cancer cells, and the reduction of proliferation in HEp-2 cancer cells induced by the dicationic one, make this class of compounds promising for future biological applications.

Facile Synthesis and Chain-Length Dependence of the Optical and Structural Properties of Diketopyrrolopyrrole-Based Oligomers.

Here, we report the synthesis, optical properties, and solid-state packing of monodisperse oligomers of diketopyrrolopyrrole (DPP) up to five repeating units. The optical properties of DPP oligomers in solution and the solid state were investigated by a combination of steady-state and transient spectroscopy. Transient absorption spectroscopy and time-correlated single photon counting (TCSPC) measurements show that the fluorescence lifetime decreases with an increase in the oligomer size from monomer to trimer, thereby reaching saturation for pentameric DPP oligomers. The solid-state packing and crystallinity were probed by using advanced techniques, which included grazing incidence small-angle X-ray scattering (GISAXS) and X-ray diffraction (XRD) to elucidate the structure-property trend. Collectively, our chain-length dependent studies establish the fundamental correlation between the structure and property and provide a comprehensive understanding of the solid-state properties in DPP-DPP based conjugated systems.

Concentration dependence of luminescence efficiency of Dy3+ ions in strontium zinc phosphate glasses mixed with Pb3 O4.

In this work we synthesized SrO-ZnO-P2 O5 glasses mixed with Pb3 O4 (heavy metal oxide) and doped with different amounts of Dy2 O3 (0.1 to 1.0 mol%). Subsequently their emission and decay characteristics were investigated as a function of Dy2 O3 concentration. The emission spectra exhibited three principal emission bands in the visible region corresponding to 4 F9/2  â†’ 6 H15/2 (482 nm), 6 H13/2 (574 nm) and 6 H11/2 (663 nm) transitions. With increase in the concentration of Dy2 O3 (upto 0.8 mol%) a considerable increase in the intensity of these bands was observed and, for further increase, quenching of photoluminescence (PL) output was observed. Using emission spectra, various radiative parameters were evaluated and all these parameters were found to increase with increase in Dy2 O3 concentration. The Y/B integral emission intensity ratio of Dy3+ ions evaluated from these spectra exhibited a decreasing trend with increase in the Dy2 O3 concentration up to 0.8 mol%. Quenching of luminescence observed in the case of the glasses doped with 1.0 mol% is attributed to clustering of Dy3+ ions. The quantitative analysis of these results together with infra-red (IR) spectral studies indicated that 0.8 mol% is the optimum concentration of Dy3+ ions needed to achieve maximum luminescence efficiency. Copyright © 2016 John Wiley & Sons, Ltd.

The dark side of hydrogen bonds in the design of optical materials: a charge-density perspective.

A combined investigation of the structural, electronic, and optical properties of three crystalline nonaaqualanthanoid(III) triflates, [Ln(H2 O)9 (CF3 SO3 )3 ], has provided unambiguous experimental evidence for charge redistribution in the first coordination sphere of a lanthanide ion as a result of hydrogen bonds with outer-sphere anions. As well as resulting in charge transfer from the noncoordinated anions to the coordinated water molecules, these hydrogen bonds give rise to a new excited state, an hydrogen-bond-induced charge-transfer state, which is observed experimentally for the first time. This state was shown to be responsible for the previously unknown negative aspect of hydrogen bonds with a lanthanide-bound water molecule: rather than increasing the luminescence efficiency of the complex, they can lead to additional quenching that is unfavorable for the task-specific design of optical materials.

A novel strategy for the synthesis of samarium/europium-metal organic frameworks, and their utilization for detection of Cr3+, Pb2+, and acetone as a luminescent sensor with superior selectivity and sensitivity properties.

With outstanding detection selectivity and sensitivity characteristics, samarium/europium-metal organic frameworks (Sm/Eu-MOF) is capable of functioning as a versatile light-emitting sensor particularly for detecting acetone, Cr3+, and Pb2+ in aqueous environment. While considering maximum detectable concentrations of 0.85 µM, 0.46 µM, and 1.04 µM, respectively, competitive energy interactions for acetone, absorption of energy for Cr3+, and substitution of ions for Pb2+ are the elucidated mechanisms of detecting these substances by Sm/Eu-MOF. Successful formulation and synthesis of a core-shell structured Sm/Eu-MOF, which has endurance to acid/alkali conditions and hydration/heat-stability, can be accomplished by utilizing Samarium and Europium nitrate ions, terephthalic acid, and 2, 5-furandicarboxylic acid. The recovery rate of acetone, Cr3+, and Pb2+ detection from real samples were 95.0-101.0 %, 99.8-101.0 %, and 99.9-104.0 %, respectively.

Near-Complete Suppression of NIR-II Luminescence Quenching in Halide Double Perovskites for Surface Functionalization Through Facet Engineering.

Lanthanide-based NIR-II-emitting materials (1000-1700 nm) show promise for optoelectronic devices, phototherapy, and bioimaging. However, one major bottleneck to prevent their widespread use lies in low quantum efficiencies, which are significantly constrained by various quenching effects. Here, a highly oriented (222) facet is achieved via facet engineering for Cs2NaErCl6 double perovskites, enabling near-complete suppression of NIR-II luminescence quenching. The optimally (222)-oriented Cs2Ag0.10Na0.90ErCl6 microcrystals emit Er3+ 1540 nm light with unprecedented high quantum efficiencies of 90 ± 6% under 379 nm UV excitation (ultralarge Stokes shift >1000 nm), and a record near-unity quantum yield of 98.6% is also obtained for (222)-based Cs2NaYb0.40Er0.60Cl6 microcrystallites under 980 nm excitation. With combined experimental and theoretical studies, the underlying mechanism of facet-dependent Er3+ 1540 nm emissions is revealed, which can contribute to surface asymmetry-induced breakdown of parity-forbidden transition and suppression of undesired non-radiative processes. Further, the role of surface quenching is reexamined by molecular dynamics based on two facets, highlighting the drastic two-phonon coupling effect of a hydroxyl group to 4I13/2 level of Er3+. Surface-functionalized facets will provide new insights for tunable luminescence in double perovskites, and open up a new avenue for developing highly efficient NIR-II emitters toward broad applications.

Selective Detection of Chromate and Permanganate Ions Using Gallic Acid Capped CaF2:Tb3+ Nanocrystals.

In this study, we have developed ligand-sensitized Ln3+-doped nanocrystals (NCs) for the selective sensing of Cr2O72- and MnO4- ions in nanomolar concentrations. This is accomplished with the gallic acid capped-CaF2:Tb3+ NCs. These NCs display bright green emission through an efficient energy transfer from surface functionalized gallic acid molecules to Tb3+ ions upon UV light excitation. The luminescence emissions from Tb3+ ions are selectively quenched by the addition of Cr2O72- and MnO4- anions. The reduction in the luminescence intensity is found to be quite selective, as the addition of other strong oxidizing species (I-, F-, Br-, Cl-, PO32-, SO42-, VO3-, WO42-, IO3-, ClO4-,) had minimal impact on the luminescence intensity of Tb3+ ions. The calculated limit of detection from the experimental results (for the 3/slope criterion) is 77 nM and 55 nM for K2Cr2O7 and KMnO4, respectively. The findings show that tuning the resonance energy transfer (RET) between analytes and Tb3+ inside the NCs serves as a tool for the detection of dichromate and permanganate ions selectively.

An electrochemiluminescence biosensor based on Graphitic carbon nitride luminescence quenching for detection of AFB1.

Based on graphite-like carbon nitride (g-CN) nanocomposites coupled with aptamer, a regenerable electrochemiluminescence (ECL) biosensor is developed for the quantitative detection of aflatoxin B1 (AFB1). In the existence of AFB1, the structure of the aptamer changed into a loop, and the original ECL intensity was reduced owing to the enhancement of luminescence quenching between the ferrocene modified at the end of the aptamer and the luminescent substrate g-CN. Moreover, AFB1 with oxidation state could also react with high energy state g-CN, leading to further reduction of the electrochemiluminescence signal. At optimum conditions, ECL intensity was decreased in linearity with an AFB1 concentration range from 0.005 ng/mL to 10 ng/mL, and the minimum detectable concentration was down to 0.005 ng/mL, which realized trace detection demand with high sensitivity. It was selective for AFB1 and its performance had been verified on rice samples, which indicated a promising applying prospect of non-enzymatic electrochemiluminescence AFB1 detection.

Effects of Low-Frequency Randomly Polarized Electromagnetic Radiation, as Revealed upon Swelling of Polymer Membrane in Water with Different Isotopic Compositions.

Photoluminescence from the surface of Nafion polymer membrane upon swelling in water under irradiation by electromagnetic waves at a frequency of 100 MHz was studied. In these experiments, natural deionized (DI) water with a deuterium content of 157 ppm and deuterium-depleted water (DDW, deuterium content is 1 ppm) were explored. We have studied for the first time the effect of linearly and randomly polarized low-frequency electromagnetic radiation on the luminescence excitation. To obtain low-frequency electromagnetic radiation with random polarizations, anisotropic solid submicron-sized particles, which result in depolarization effects upon scattering of the initially linearly polarized radiation, were used. We compared two types of colloidal particles: spherically symmetric (isotropic) and elongated (anisotropic). If the radiation is linearly polarized, the intensity of luminescence from the Nafion surface decreases exponentially as the polymer is soaked, and such a behavior is observed both in natural DI water and DDW. When spherically symmetric submicron-sized particles are added to a liquid sample, the luminescence intensity also decreases exponentially upon swelling in both natural DI water and DDW. At the same time, when anisotropic submicron-sized particles are added to DI water, random jumps in the luminescence intensity appear during swelling. At the same time, the exponential decrease in the luminescence intensity is retained upon swelling in DDW. A qualitative theoretical model for the occurrence of random jumps in the luminescence intensity is presented.

Electrically Driven Sub-Micrometer Light-Emitting Diode Arrays Using Maskless and Etching-Free Pixelation.

For decades, group-III-nitride-based light-emitting diodes (LEDs) have been regarded as a light emitting source for future displays by virtue of their novel properties such as high efficiency, brightness, and stability. Nevertheless, realization of high pixel density displays is still challenging due to limitations of pixelation methods. Here, a maskless and etching-free micro-LED (µLED) pixelation method is developed via tailored He focused ion beam (FIB) irradiation technique, and electrically driven sub-micrometer-scale µLED pixel arrays are demonstrated. It is confirmed that optical quenching and electrical isolation effects are simultaneously induced at a certain ion dose (≈1014 ions cm-2 ) without surface damage. Furthermore, highly efficient µLED pixel arrays at sub-micrometer scale (square pixel, 0.5 µm side length) are fabricated. Their pixelation and brightness are verified by various optical measurements such as cathodo-, photo-, and electroluminescence. It is expected that the FIB-induced optical quenching and electrical isolation method can pioneer a new defect engineering technology not only for µLED fabrication, but also for sub-micrometer-scale optoelectronic devices.

One-dimensional Europium-coordination polymer as luminescent sensor for highly selective and sensitive detection of 2,4,6-trinitrophenol.

Three isostructural lanthanide coordination polymers (LnCPs), [Ln(L)6(DMF)]n {HL = 2-(2-formylphenoxy) acetic acid, Ln = Sm (1); Eu (2); Tb (3)} have been synthesized by solvothermal reaction and characterized. Single crystal analyses revealed that the architectures of these LnCPs own one dimensional chain which can be further packed into two-dimensional architectures by hydrogen bonds. Moreover, these LnCPs can offer strategically placed uncoordinated formyl groups, which may act as hydrogen-bond acceptor in the sensing of nitro explosives. Luminescence measurements reveal that LnCPs 2 and 3 exhibit strong luminescence in solid states. LnCP 2 shows quick, highly selective and sensitive detection of 2,4,6-trinitrophenol (TNP) with the high quenching constant (2.6 × 104 M-1) and low detection limit (3.39 µM), which indicates that LnCP 2 is more efficient than most of Eu-based coordination polymers for the sensing of TNP. Furthermore, LnCP 2 represents the first example of one-dimensional Eu-based sensors with formyl group as hydrogen-bonding site in the detection of TNP.

CdII-based compound as a multi-responsive fluorescent probe for sensing FeIII cations and CrVI oxyanions.

A new luminescent CdII compound, poly[[µ2-1,4-bis(1H-imidazol-1-yl)benzene]{µ2-5-[(3-carboxylphenoxy)methyl]isophthalato}cadmium(II)], [Cd(C16H10O7)(C12H10N4)]n or [Cd(HL)(1,4-bib)]n {H3L is 5-[(3-carboxyphenoxy)methyl]isophthalic acid and 1,4-bib is 1,4-bis(1H-imidazol-1-yl)benzene}, I, has been synthesized successfully from CdII and a semirigid tricarboxylic ligand under hydrothermal conditions. Structure analysis shows that I is a two-dimensional structure with the point symbol {44.62}. The three-dimensional framework is constructed by O-H...O hydrogen bonds and π-π stacking interactions. Furthermore, the obtained CdII compound displays high solvent stability and excellent thermal stability, as shown by powder X-ray diffraction and thermogravimetry measurements. Studies of the luminescence properties reveal that compound I can act as a promising luminescent sensor for detecting FeIII cations and CrVI oxyanions with high selectivity and low detection limits (0.19 µM for Fe3+ and 1.13 µM for Cr2O72-), and is additionally free from the interference of other ions. The mechanism of selective quenching was studied by measuring the UV-Vis absorption of the host compound and the target analytes.

Solution-processable carbon dots with efficient solid-state red/near-infrared emission.

Carbon dots (CDs) emerge as promising luminescent materials for potential applications in optoelectronics on basis of their merits including low cost, eco-friendliness and strong, color-tunable photoluminescence (PL). However, the research on solid-state emissive CDs is still at the primary stage because of the aggregation-caused quenching (ACQ) of PL and their poor film-formation ability. In this work, we produce CDs with branched-polyethylenimine (b-PEI) chemically functionalized on the surfaces. The thus newly synthesized P-CDs successfully overcome the bottleneck of ACQ effect and display efficient red and NIR emission in aggregate state. Under the excitation of 520 nm, a strong red emission (maxima of 640 nm) with a high photoluminescence quantum yield (PLQY) of 21% was observed for the P-CDs in neat film. Moreover, this design strategy endows the P-CDs with good film-formation ability via solution spin-coating, which significantly increases its value for the film-based optoelectronic devices.