Luminescence Detection Research Articles

A water-stable molecular cadmium phosphonate bearing 2-(2-pyridyl)benzimidazole as a highly sensitive luminescence sensor for the selective detection of bisphenol AF and bisphenol B

A highly water-stable molecular cadmium phosphonate bearing 2-(2-pyridyl)benzimidazole has been used as a sensor platform for the luminescence detection of bisphenol AF (BPAF) and bisphenol B (BPB) in water with good sensitivity and selectivity.

Heterometallic MOFs constructed from thiophene and furandicarboxylate ligands for heavy metal luminescence sensing.

Rational design of a series of new heterometallic MOFs was carried out by the judicious choice of the corresponding synthesis conditions and ligand geometry. Three heterometallic MOFs (H2NMe2)[LiZn(dmf)(tdc)2]·DMF·H2O (1), [{LiZn}2Li2Zn2(dmf)6(tdc)6]·6DMF·H2O (2) and [Li2Zn2(dmf)2(fdc)3]·2DMF·2H2O (3) were obtained on the basis of the pre-synthesized pivalate complex [Li2Zn2(py)2(piv)6]. The angle between carboxylic groups greatly affects the possibility of retaining the initial tetranuclear node in the structure of the obtained MOFs. Compound 3 demonstrates permanent porosity with a calculated BET surface area value of 287 m2 g-1. Compounds 2 and 3 are capable of heavy metal sorption from their nitrate solution, and a significant flare-up of the luminescence of the obtained inclusion compounds is observed, where the quantum yield of luminescence increases by an order of magnitude in the case of cadmium inclusion.

An excellent water-stable 3D Zn-MOF with 8-fold interpenetrated diamondoid topology showing "turn-on/turn-off" luminescent detection of Al3+ and SNT in aqueous media.

The effective detection of Al3+ and antibiotics pollutants is crucial for environmental protection and human health due to their high toxicity and nondegradability, but it is still currently challenging. In this work, a methyl-decorated acylamide-containing dicarboxylate ligand H2L was elaborately designed and successfully synthesized, which was further employed to react with Zn(ii) ions and dpe ligands to construct a new luminescent Zn-MOF, namely {[Zn(L)(dpe)]·DMF·3H2O}n (1). X-ray crystallography reveals that MOF 1 is a 3D 8-fold [4 + 4] interpenetrated diamondoid framework with isolated DMF and water molecules in the pores, in which the uncoordinated acylamide groups are found and facilitate the Zn-MOF to recognize analyte molecules. The activated solvent-free MOF sample (denoted as 1a) exhibits excellent water stability and good luminescent performance. The luminescence sensing experiments show that 1a could behave as a bi-responsive chemical sensor for “turn-on” and “turn-off” luminescent detection of Al3+ and SNT in aqueous media, respectively. The sensing mechanisms have also been discussed. Furthermore, MOF 1a was successfully applied to the effective determination of Al3+ and SNT in real water samples. This represents, to our knowledge, the first example of a MOF material for “turn-on” and “turn-off” luminescent detection of Al3+ and SNT in water, which will promote the practical application of water-stable luminescent MOF sensors in monitoring metal ions and antibiotics pollutants in the environmental water matrices.

Sunlight assisted SCSC dimerization of a 1D coordination polymer impacts the selectivity of Pd(ii) sensing in water

A one-dimensional coordination polymer (1D CP) [Cd(4-nvp)2(5-ssa)]·(4-nvp) (1) [4-nvp = 4-(1-naphthylvinyl)pyridine and 5-ssa = 5-sulfosalicylic acid] undergoes topochemical [2+2] cycloaddition by sunlight irradiation to generate a two-dimensional (2D) CP [Cd(rctt-4-pncb)0.5(4-nvp)(5-ssa)]·(4-nvp) (1') [rctt-4-pncb = 1,3-bis(4'-pyridyl)-2,4-bis(naphthyl)cyclobutane] in a single-crystal to single-crystal manner. Interestingly, 1' can be reverted back to 1 by heating and both the CPs selectively recognize Pd2+ in aqueous medium; however, the limit of detection is improved after photodimerization.

Covalent-coordination tandem functionalization of a metal-organic framework (UiO-66) as a hybrid probe for luminescence detection of trans,trans-muconic acid as a biomarker of benzene and Fe3.

By means of post-synthetic treatment on the UiO-66 derivative with -SO3H, a novel luminescent hybrid material named Tb3+@UiO-66-SO3H has been prepared simply and efficiently. Given its wonderful luminescence properties like intense green emission, a long lifetime, a robust structure and photostability, it is further developed as a fluorescent probe for the sensing of trans,trans-muconic acid (tt-MA, a biomarker of benzene) and Fe3+, which are closely related to human health. Notably, Tb3+@UiO-66-SO3H shows an outstanding recognition ability for Fe3+ among common cations with a low detection limit (0.11 μM, 0.006 ppm). More importantly, Tb3+@UiO-66-SO3H can realize highly sensitive and selective detection of tt-MA (detection limit, 0.58 μM, 0.083 ppm). Besides, this rapid response probe is facilely prepared, non-toxic and reusable, showing the potential of Tb3+@UiO-66-SO3H in the practical monitoring of tt-MA and Fe3+.

Construction of a high-nuclearity Nd(III) nanoring for the NIR luminescent detection of antibiotics.

One NIR luminescent 14-metal Nd(iii) nanoring (1, molecular size: 1.0 × 2.2 × 2.6 nm) was obtained from a rigid tridentate ligand, which can absorb and transfer light energy to the Nd(iii) ions. 1 shows interesting luminescence sensing activity to antibiotics, in particular to NFAs with high sensitivity due to the inner filter effect. The quenching constants and the limits of detection of 1 to NFAs are 1.05 × 104 M-1-2.33 × 104 M-1 and 3.05 μM-6.75 μM, respectively. The high fluorescence sensitivities of 1 to NFAs are not changed by the existence of other antibiotics. It also exhibits high sensitivity in the luminescent detection of NFAs contained in real antibiotic drugs.

Исследование славянского пергамена методами спектроскопии комбинационного рассеяния света и люминесцентной спектроскопии

In the present article the pigments palette of a parchment handwritten fragment from the collection of Finnish fragments N 29 (Library of the Russian Academy of Sciences, Finnish fragment 29, old code - 4.9.28), dating from the XIV century, was investigated. This manuscript has not been restored earlier. With the aid of Raman spectroscopy technique it was found the use of cinnabar for red shades, the mixture of indigo and gypsum pigments in various ratios for blue shades and a mixture of sulfur-arsenic pigments (orpiment and pararealgar) for yellow shades. It was performed the study of the characteristic luminescence detection capability of the pigments at the real (non-model) samples, when excited by laser radiation of various wavelengths.

Bifunctional luminescent Eu metal–organic framework for sensing nitroaromatic pollutants and Fe3+ ion with high sensitivity and selectivity

In recent years, heavy metal ions and nitroaromatic explosives in environmental pollutants have been a serious threat to human health due to their high toxicity, carcinogenicity, and nondegradability. The detection of metal ions and nitroaromatics has become an urgent problem. In this paper, a new water stable luminescent Eu‐based metal–organic framework ([Eu(L)(DMF)2]n) was prepared by the reaction of rigid ligand H3L (3,5‐bis‐(3‐carboxyphenoxy)benzoic acid) and Eu (NO3)3·6H2O under solvothermal conditions. Luminescent detection of the nitroaromatic compounds and metal ions showed that the complex had high sensitivity to Fe3+, o‐nitrophenol, p‐nitrophenol, and m‐nitrophenol.

Detection of singlet oxygen luminescence for experimental corneal rose bengal photodynamic antimicrobial therapy.

Rose bengal photodynamic antimicrobial therapy (RB-PDAT) treats corneal infection by activating rose bengal (RB) with green light to produce singlet oxygen (1O2). Singlet oxygen dosimetry can help optimize treatment parameters. We present a 1O2 dosimeter for detection of 1O2 generated during experimental RB-PDAT. The system uses a 520 nm laser and an InGaAs photoreceiver with bandpass filters to detect 1O2 luminescence during irradiation. The system was validated in RB solutions and ex vivo in human donor eyes. The results demonstrate the feasibility of 1O2 dosimetry in an experimental model of RB-PDAT in the cornea.

Targeted Protein Degradation Phenotypic Studies Using HaloTag CRISPR/Cas9 Endogenous Tagging Coupled with HaloPROTAC3.

To assess the role of a protein, protein loss phenotypic studies can be used, most commonly through mutagenesis RNAi or CRISPR knockout. Such studies have been critical for the understanding of protein function and the identification of putative therapeutic targets for numerous human disease states. However, these methodological approaches present challenges because they are not easily reversible, and if an essential gene is targeted, an associated loss of cell viability can potentially hinder further studies. Here we present a reversible and conditional live‐cell knockout strategy that is applicable to numerous proteins. This modular protein‐tagging approach regulates target loss at the protein, rather than the genomic, level through the use of HaloPROTAC3, which specifically degrades HaloTag fusion proteins via recruitment of the VHL E3 ligase component. To enable HaloTag‐mediated degradation of endogenous proteins, we provide protocols for HaloTag genomic insertion at the protein N or C terminus via CRISPR/Cas9 and use of HaloTag fluorescent ligands to enrich edited cells via Fluorescence‐Activated Cell Sorting (FACS). Using these approaches, endogenous HaloTag fusion proteins present in various subcellular locations can be degraded by HaloPROTAC3. As detecting the degradation of endogenous targets is challenging, the 11‐amino‐acid peptide tag HiBiT is added to the HaloTag fusion to allows the sensitive luminescence detection of HaloTag fusion levels without the use of antibodies. Lastly, we demonstrate, through comparison of HaloPROTAC3 degradation with that of another fusion tag PROTAC, dTAG‐13, that HaloPROTAC3 has a faster degradation rate and similar extent of degradation. © 2020 The Authors. Basic Protocol 1: CRISPR/Cas9 insertion of HaloTag or HiBiT‐HaloTag Basic Protocol 2: HaloPROTAC3 degradation of endogenous HaloTag fusions

A Monitor Calibrator as a Portable Tool for Determination of Luminescent Compounds

A monitor calibrator has been tested as a portable, available, and cost-effective tool for the detection of luminescence. Prospects of this device as an all-sufficient analog of an analytical fluorometer have been outlined. Its ability to determine luminescent compounds was demonstrated by the example of rhodamine 3B and fluorescein. The determination is based on simultaneous impulse irradiation of a fluorescent sample with the incorporated continuous-spectrum light emitter in the visible and near UV ranges and registration of the luminescence. The appropriate cuvettes for the analysis and the device sealing film were chosen. The lowest relative detection limit for the developed approach was 0.03 μmol L-1 for rhodamine 3B and 0.01 μmol L <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-1</sup> for fluorescein; the lowest absolute detection limits were 0.01 and 0.002 nmol for rhodamine 3B and fluorescein, respectively. Using the proposed approach, it was possible to determine the luminescent compounds in tap water.

A porous Cd-based metal-organic framework for sensitive and selective detection of aspartic acid/Ag+ in aqueous medium

The development of a fast and stable luminescence detection method is of great significance to people's health and the protection of the ecological environment. In this work, a porous three-dimensional (3D) Cd-based metal-organic framework (MOF1) has been synthesized by the reaction of tri(p-carboxyphenyl)phosphane oxide (H3L) and 1,4-bis(pyrid-4-yl)benzene (1,4-bpb) with Cd2+ ions based on the mixed-ligand strategy, and characterized by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and scanning electron microscope (SEM), etc. The luminescence experiments of MOF1 for amino acids and cations showed that MOF1 has highly sensitive and selective recognition for aspartic acid/Ag+ in aqueous medium. Meanwhile, the recognition mechanism of MOF1 for aspartic acid/Ag+ was analyzed by a series of experiments, the results indicate that the energy gap between HOMO energy values of H3L and aspartic acid/Ag+ is recognition impetus of MOF1 for aspartic acid by enhancement luminescence and for Ag+ by luminescence quenching, the sensing processes of MOF1 for aspartic acid and Ag+ ions are dynamic and static respectively by fluorescence lifetimes. Furthermore, the cycle and anti-interference experiments indicate that MOF1 has good luminescence stability and high sensing selectivity for aspartic acid and Ag+. The above results indicate that MOF1 has potential applications in recognizing aspartic acid and Ag+ in aqueous medium.

Sensitivity differences among five species of aquatic fungi and fungus-like organisms for seven fungicides with various modes of action.

Five species of aquatic fungi and fungus-like organisms were used for toxicity assays with seven fungicides to determine the differences in species sensitivity. A microplate toxicity assay with adenosine triphosphate luminescence detection was used as an efficient and economical high-throughput assay. The obtained toxicity data were standardized based on the species sensitivity distribution method. Species sensitivity differed among the fungicides: Rhizophydium brooksianum was most sensitive to hydroxyisoxazole, isoprothiolane, and ferimzone; Chytriomyces hyalinus was most sensitive to tricyclazole; Sporobolomyces roseus was most sensitive to ipconazole; Aphanomyces stellatus was most sensitive to orysastrobin and kasugamycin. Tetracladium setigerum was not the most sensitive species to any of the tested fungicides. The ranges of EC50s to fungal species were lower than to other aquatic organisms (primary producers, invertebrates, and vertebrates) for hydroxyisoxazole, kasugamycin, isoprothiolane, ipconazole, and ferimzone. These results suggest the usefulness of a battery of fungal species to assess the ecological effects of fungicides.

A Ruthenium(II) complex-based probe for colorimetric and luminescent detection and imaging of hydrogen sulfide in living cells and organisms

The development of reliable bioanalytical probes for sensitive and specific detection of hydrogen sulfide (H2S) plays important role for better understanding the roles of this biomolecule in living cells and organisms. Taking advantages of unique photophysical properties of ruthenium(II) (Ru(II)) complex, this work presents the development of a responsive Ru(II) complex probe, Ru-PNBD, for colorimetric and luminescent analysis of H2S in living cells and organisms. In aqueous solution, Ru-PNBD is yellow color and non-luminescent because of the photoinduced electron transfer (PET) process from Ru(II) complex luminophore to NBD moiety. The H2S-triggered specific nucleophilic substitution reaction with Ru-PNBD cleaves the NBD moiety to form pink NBD-SH and highly luminescent Ru-PH. The color of the solution thus changes from yellow to pink for colorimetric analysis and the emission intensity is about 65-fold increased for luminescent analysis. Ru-PNBD has high sensitivity and selectivity for H2S detection, low cytotoxicity and good permeability to cell membrane, which allow the application of this probe for H2S imaging in living cells, Daphnia magna, and larval zebrafish. Collectively, this work provides a useful tool for H2S analysis and expands the scope of transition metal complex probes.

Magnetic Nanoparticle-Based Ligand Replacement Strategy for Chemical Luminescence Determination of Cholesterol.

Determination of serum cholesterol (Chol) is important for disease diagnosis, and has attracted great attention during the last few decades. Herein, a new magnetic nanoparticle-based ligand replacement strategy has been presented for chemical luminescence detection of Chol. The detection depends on ligand replacement from ferrocene (Fc) to Chol through a β-cyclodextrin (β-CD)–based host–guest interaction, which releases Fc–Hemin as a catalyst for the luminol/hydrogen peroxide chemical luminescence system. More importantly, the luminescence signal can be captured by the camera of a smartphone, thus realizing Chol detection with less instrument dependency. The limit of detection of this method is calculated to be 0.18 μM, which is comparable to some of the developed methods. Moreover, this method has been used successfully to quantify Chol from serum samples with a simple extraction process.

Two Zn(II)-organic frameworks based on “V”-shaped terpyridine ligand and dicarboxylic ligands: Fascinating architectures and efficient luminescent aqueous-phase dual-responsive detection

A “V”-shaped terpyridine ligand 3,3’:5′,3″-terpyridine (L) was firstly applied to construct metal-organic frameworks. Two Zn-MOFs, [Zn2(L) (BDC)2(H2O)]n (1) and {[Zn(L) (ISO)]·H2O}n (2) (H2BDC ​= ​terephthalic acid, H2ISO ​= ​isophthalic acid) had been successfully synthesized by L and auxiliary dicarboxylic ligands. Structurally, 1 features an unprecedented (3,3,8)-connected framework constructed from tridentate L units, mononuclear Zn units, binuclear [Zn2(CO)2] units and BDC2− bridges. While 2 shows a rare (3,5)-connected architecture assembled from tridentate L units, mononuclear Zn units and ISO2− bridges. The different structures and topological diversities between 1 and 2 can be attributed to different twist angles between pyridine rings in L and distinct bridging angles from auxiliary ligands. Moreover, luminescent sensing experiments exhibit that 1 can act as a promising dual-responsive sensor for detecting TNP and Fe3+ in aqueous phase with high efficiency. The luminescence test paper was successfully developed to detect TNP for the practical applications. In addition, the emission quenching mechanisms of 1 towards TNP and Fe3+ were elucidated.

Soldered Joints of Piezoelectric Products

The paper considers issues related to the use of capillary luminescent flaw detection for monitoring glass-metal soldered joints of piezoelectric products. Standard methods of leakproofness testing of piezoelectric products are analysed; the framework for the applicability of each of them at the stages of the life cycle of piezoelectric productsis established. Based on the results of the studies, a capillary luminescent control method was chosen to check the tightness of glass-metal soldered joints in piezoelectric products. The stages of conducting a capillary luminescent method for monitoring glass-metal soldered joints of piezoelectric products are presented. A method for monitoring the tightness of piezoelectric products using the capillary luminescent method has been developed.

Revealing Interplay of Defects in SnO2 Quantum Dots for Blue Luminescence and Selective Trace Ammonia Detection at Room Temperature.

Defect chemistry in SnO2 is well established for resistive sensors but remains to be elusive for photoluminescence (PL) sensors. It demands a comprehensive understanding of the role of cationic and oxygen defects as well as the creation of abundant such defects to provide a selective PL signal. To accomplish it, SnO2 quantum dots (QDs ∼ 2.4 nm) are prepared without a capping agent along with other dimensions. Then, the relationship of defects with the blue-emission PL is unfolded by electron energy loss spectroscopy, lifetime measurements, X-ray absorption, and Raman spectroscopic measurements. The defects acting as Lewis acid sites are utilized for selective ammonia detection. Huge enhancements of the obscured blue luminescence at 2.77 and 2.96 eV from the SnO2 QDs are observed because of interaction with ammonia. The linear variation of PL intensities with analyte concentrations and the recovery of the sensor are elaborated with detection up to 5 ppm. The interplay of defects in SnO2 is further established theoretically for site-specific interactions with ammonia by density functional theory (DFT) calculations. Thus, the unique mechanism revealed for the superlative performance of the PL sensor with uncapped SnO2 QDs provides a novel platform for defect-engineering-based optoelectronic applications.

Luminescence of Cypridina Luciferin in the Presence of Human Plasma Alpha 1-Acid Glycoprotein

The enzyme Cypridina luciferase (CLase) enables Cypridina luciferin to emit light efficiently through an oxidation reaction. The catalytic mechanism on the substrate of CLase has been studied, but the details remain to be clarified. Here, we examined the luminescence of Cypridina luciferin in the presence of several proteins with drug-binding ability. Luminescence measurements showed that the mixture of human plasma alpha 1-acid glycoprotein (hAGP) and Cypridina luciferin produced light. The total value of the luminescence intensity over 60 s was over 12.6-fold higher than those in the presence of ovalbumin, human serum albumin, or bovine serum albumin. In the presence of heat-treated hAGP, the luminescence intensity of Cypridina luciferin was lower than in the presence of intact hAGP. Chlorpromazine, which binds to hAGP, showed an inhibitory effect on the luminescence of Cypridina luciferin, both in the presence of hAGP and a recombinant CLase. Furthermore, BlastP analysis showed that hAGP had partial amino acid sequence similarity to known CLases in the region including amino acid residues involved in the drug-binding ability of hAGP. These findings indicate enzymological similarity between hAGP and CLase and provide insights into both the enzymological understanding of CLase and development of a luminescence detection method for hAGP.

Facile Dual Enhanced Modes of Nanoparticles/Sodium Dodecyl Sulfate for Luminescent Detection of Vitamin C in Commercial Fruit Juices

The present study suggested three different highly sensitive luminescent systems based on the employment of silver nanoparticles (NPs), copper oxide nanoparticles and gold nanoparticles in the presence of micellar medium sodium dodecyl sulfate (SDS) for the detection of ascorbic acid in some fruit juices. The fluorescence spectral behavior of ascorbic acid was detected at λem of 420 nm after λex at 350 nm in the presence of acetate buffer (pH 3). Under optimized experimental conditions, the suggested spectroflourimetric systems displayed excellent linearity over concentration ranges of 1.0 × 10–9–1.0 × 10–2, 1.0 × 10–7–1.0 × 10–3 and 1.0 × 10–6–1.0 × 10–3 M with lower limits of detection of 1.0 × 10–10, 5 × 10–8 and 5 × 10–7 M for SDS−AgNPs, SDS−CuONPs and SDS−AuNPs systems, respectively. The suggested approaches were successfully used to detect ascorbic acid in its bulk powder and in some commercial fruit juices.