A near-infrared fluorescent probe with a substantial Stokes shift designed for the detection and imaging of ß-galactosidase within living cells and animals.

ß-Galactosidase serves as a pivotal biomarker for both cancer and cellular aging. The advancement of fluorescent sensors for tracking ß-galactosidase activity is imperative in the realm of cancer diagnosis. We have designed a near-infrared fluorescent probe (PTA-gal) for the detection of ß-galactosidase in living systems with large Stokes shifts. PTA-gal exhibits remarkable sensitivity and selectivity in detecting ß-galactosidase, producing near-infrared fluorescent signals with a remarkably low detection limit (2.2 × 10-5 U/mL) and a high quantum yield (0.30). Moreover, PTA-gal demonstrates biocompatibility and can effectively detect ß-galactosidase in cancer cells as well as within living animals.

Ratiometric Fluorescent Probe for the Detection of Nanomolar Phosgene in Solution and Gaseous Phase: Advancing Crime Detection Applications.

Phosgene, an exceptionally hazardous gas, poses a grave concern for the health and safety of the general public. The present study describes a fluorescent ratiometric probe for phosgene employing 2-(naphthalen-2-yl) benzo[d]oxazol-5-amine (NOA) with an amino group as the recognition site. NOA detects phosgene through the intramolecular charge transfer mechanism. The electron-rich amine group of NOA attacks the electrophilic carbonyl group of phosgene, resulting in a quick response within 20 s. NOA demonstrates a low detection limit of 60 nM while maintaining high selectivity and sensitivity toward phosgene. The final product was isolated and verified by nuclear magnetic resonance spectroscopy. The probe can detect phosgene not just quickly in a solution environment but also in its solid state. The probe's applications in fingerprint imaging and bioimaging are also demonstrated.

The Responses of Bioactive Betanin Pigment and Its Derivatives from a Red Beetroot (Beta vulgaris L.) Betalain-Rich Extract to Hypochlorous Acid.

Neutrophils produce hypochlorous acid (HOCl) as well as other reactive oxygen species as part of a natural innate immune response in the human body; however, excessive levels of HOCl can ultimately be detrimental to health. Recent reports suggest that betacyanin plant pigments can act as potent scavengers of inflammatory factors and are notably effective against HOCl. Comparison of the in vitro anti-hypochlorite activities of a novel betalain-rich red beetroot (Beta vulgaris L.) extract with its pure betalainic pigments revealed that the extract had the highest anti-hypochlorite activity, far exceeding the activity of all of the betalainic derivatives and selected reference antioxidants. This suggests that it may be an important food-based candidate for management of inflammatory conditions induced by excessive HOCl production. Among all pigments studied, betanidin exhibited the highest activity across the pH range.

Rapid Extraction and Analysis of Volatile Solutes with an Effervescent Tablet.

Extraction of volatile compounds from complex liquid matrices is a critical step in volatile compound analysis workflows. Recently, green chemistry principles are increasingly implemented in extraction processes. Some of the available approaches are solvent-free but still require concentration or trapping of analytes. Here, we propose effervescent tablet-induced extraction (ETIE) as a method of transferring volatile/semivolatile compounds from liquid matrices to the gas phase for analysis. This technique relies on the release of carbon dioxide produced in situ during a neutralization reaction, which occurs when a tablet is inserted into an aqueous sample matrix. In this process, many bubbles of carbon dioxide are instantly formed in the sample matrix. The bubbles rapidly extract and liberate volatile compounds from the sample. The gaseous effluent is then immediately transferred to a detector (atmospheric pressure chemical ionization mass spectrometry (MS) or gas chromatography (GC) hyphenated with MS). ETIE-GC-MS can be used for analysis of volatile compounds present in real samples. The method was validated for analysis of selected ethyl esters present in a yogurt drink. The calibration data set was linear over a range from 5 × 10-7 to 1 × 10-5 M. The limits of detection ranged from 1.51 × 10-7 to 6.82 × 10-7 M, while the recoveries ranged from 71 to 118%. Inter- and intraday precision of selected ethyl esters in aqueous solution was satisfactory (relative standard deviation, 3.6-18.3%). Furthermore, it is shown that ETIE improves the performance of headspace solid-phase microextraction while eliminating the need for heating and shaking samples.

A nano-molar fluorescent turn-on probe for copper(II) detection in living cells.

The development of fluorescent probes to detect trace metal ions in biological samples has been in great need. Herein, a fluorescence turn-on sensor (PHC) was designed for highly selective detection of Cu2+ ions. The probe PHC shows weak fluorescence due to imine isomerization. With Cu2+, a significant blue emission due to Cu2+-induced oxidation of imine to a carboxylate group is observed. The turn-on process is observed with a 63-fold increase of fluorescence quantum yield (from 0.004 to 0.252). The emission intensity has a good linear relation at Cu2+ concentrations of 0-40 µM. The detection limit is estimated as 8 nM (S/N = 3). The maximum emission change induced by Cu2+ is found in the pH range of 6.5-8.0. The probe PHC can be applied in detecting Cu2+ in living cells monitored by confocal fluorescence microscopy imaging.

A far-red to NIR emitting ultra-sensitive probe for the detection of endogenous HOCl in zebrafish and the RAW 264.7 cell line.

Fluorescence imaging is a dynamic tool for monitoring the functions of biomolecules in living systems. Probes with emission in the far-red to near-infrared range have been found to demonstrate great application prospects in bioimaging due to their deep tissue penetration, low background fluorescence, minimum photodamage to the tissue and high sensitivity. The present study aimed to construct a far-red to near-infrared emitting probe (PI) bearing dicyanoisophorone coupled with a phenothiazine moiety. The probe exhibits an instant response towards HOCl with a colour change from red to yellow with a 100 fold fluorescence enhancement at 620 nm with a low detection limit (42 nM). The electron-rich sulfur atom can be oxidised by HOCl; this endows the probe with distinct selectivity over other anions as well as other reactive oxygen species. The probe demonstrates great cell permeability with low toxicity to the cell. Therefore, the probe can be effectively applied in biological systems to monitor the endogenous level of HOCl produced by PMA in living systems and in the fluorescence imaging of endogenous HOCl in zebrafish and the RAW 264.7 cell line.

Cysteamine-capped gold-copper nanoclusters for fluorometric determination and imaging of chromium(VI) and dopamine.

Highly emissive cysteamine-capped gold-copper bimetallic nanoclusters (CA-AuCu NCs) with a quantum yield of 18% were synthesized via one-pot anti-galvanic reduction. The CA-AuCu NCs were characterized by HR-TEM, XPS, FTIR, MALDI-TOF mass spectrometry, DLS, and zeta potential analyses. The NCs are shown to be viable fluorescent probes for Cr(VI) ions and dopamine (DA) via quenching of the blue fluorescence, typically measured at excitation/emission wavelengths of 350/436 nm. During DA recognition, a dark brown color appears, which is distinguishable from that of Cr(VI) detection. The aggregation induced quenching due to electron transfer was demonstrated by photoluminescence, HR-TEM, FTIR, DLS, and zeta potential interrogations. In buffer of pH 7, response is linear in the 0.2 ~ 100 µM for Cr(VI) and from 0.4 ~ 250 µM for DA. The respective detection limits are 80 and 135 nM. The method was applied to the determination of both Cr(VI) and DA in (spiked) tap, lake and sea water, and in human urine samples. The low toxicity of CA-AuCu NCs was validated by the MTT assay, and their responses to Cr(VI) ions and DA was also proven by Raw 264.7 cell imaging. Graphical abstractCysteamine capped Au-Cu nanoclusters (CA-AuCu NCs) were synthesized via one-pot anti-galvanic reduction and utilized in sensing of Cr(VI) ions and dopamine (DA) with demonstrated real/urine and cell imaging applications.

Highly Selective Detection of Cr3 + Ion with Colorimetric & Fluorescent Response Via Chemodosimetric Approach in Aqueous Medium.

So far, very few numbers of chemosensors for Cr3+ ion have been reported. However, the main drawback of reported receptors are the lack of selectivity and other trivalent cations such as Fe3+, Al3+ and anions like F- and -OAc frequently interfere with such assays. This paper present the synthesis, characterization & sensor studies of Schiff base containing naphthalene moiety which selectively detect Cr3+ ion by chemodosimetric approach. Using FT-IR, 1H NMR, 13C NMR and ESI mass spectroscopic techniques the probe was characterized. This receptor exhibit more selectivity and sensitivity towards Cr3+ than other divalent and trivalent cations like Mn2+, Zn2+, Co2+, Ni2+, Cd2+, Cu2+, Hg2+, Fe3+, and Al3+ ions. After the addition of chromium ion the receptor get change from yellow to colorless in aqueous medium. But no color change was observed on the addition of other metal ions. Using UV-Vis and PL studies, it was confirmed that the selective hydrolysis of imine group of receptor by Cr3+ ions takes place with high fluorescence enhancement that is corresponding to 1-naphthylamine. Receptor acts as selective chemodosimeter for Cr3+ ions with 2:1 stoichiometry and micro molar detection limit. This chemodosimetric approach was applied successfully for bio-imaging of HeLa cells.

A triple action chemosensor for Cu2+ by chromogenic, Cr3+ by fluorogenic and CN- by relay recognition methods with bio-imaging of HeLa cells.

A triple action chemosensor (R1) bearing a rhodamine and thiophene moiety was synthesized by a simple condensation reaction. The sensing behaviour and selectivity of the synthesized chemosensor toward metal ions were studied by UV-Vis and fluorescence spectroscopy. The chemosensor recognized Cu2+ and Cr3+ ions with significant changes in UV-Vis absorbance and fluorescence intensity. The results showed that Cr3+ induced greater fluorescence enhancement whereas Cu2+ ions bound strongly with the receptor by showing a strong absorption band at 554 nm but with weak fluorescence. A visible colour change was observed by the addition of Cu2+ and that colour change is due to the opening of the spirolactam ring triggered by the addition of Cu2+ ions. Job's plot analysis indicated a 1 : 2 and 1 : 1 binding stoichiometry between the chemosensor and Cr3+/Cu2+. Subsequently, the R1 - Cu2+ complex chemosensor was employed to detect CN- in the presence of different anions, such as F-, Cl-, Br-, I-, AcO-, H2PO4-, HSO4-, NO3- and -OH. In addition, the live cell imaging of HeLa cells using R1 and Cr3+ was demonstrated successfully.

New phenazine based AIE probes for selective detection of aluminium(iii) ions in presence of other trivalent metal ions in living cells.

Phenazine fluorophore based imidazole derivatives (S1 and S2) were synthesized and sensor studies were carried out with various cations. Aggregation induced emission (AIE) was observed selectively for Al3+ among other cations under study in case of both sensors. 1H NMR titration supported the aggregation induced emission of S2 with Al3+. ESI mass spectra successfully confirmed the aggregate formation. SEM images clearly showed the aggregation of receptor induced by Al3+ in a flower-like fashion. AIE probe was successfully applied for bio-imaging of RAW264.7 cells.

Gd2O3:RE³âº and GdAlO3:RE³âº (RE = Eu, Dy) Phosphor: Synthesis, Characterization and Bioimaging Application.

Citrate based sol­gel method is used to synthesize Gd2O3:RE³âº and GdAlO3:RE³âº (RE = Eu, Dy) phosphors. In the present work, the phosphors are characterized using the techniques like X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), diffuse reflectance spectroscopy (DRS) and photoluminescence spectroscopy (PL). Fluorescence confocal microscopy reveals the potential usage of phosphors in biological medium for biolabeling application. XRD patterns confirm the phase purity of Gd2O3 and GdAlO3. The crystallite size and lattice parameters are estimated from XRD result. FTIR spectra are used to investigate the functional group present in the phosphor. The optical emission properties imply that the emission peak positions on Eu³âº or Dy³âº ion are size and host independent. Finally, RAW 264.7 macrophages cell line is used to test the bioimaging performance of the phosphors.

Nanodiamonds conjugated to gold nanoparticles for colorimetric detection of clenbuterol and chromium(III) in urine.

Nanodiamonds were modified such that they carry thiol groups (ND-thiol). Gold nanoparticles were reacted with ND-thiol to obtain a highly stable conjugate of the type ND@AuNPs. Both ND-thiol and the ND@AuNPs were characterized by SEM, TEM, AFM, DLS, zeta potential, XPS, XRD, UV-Vis, Raman, FTIR and cytotoxicity studies. Their biocompatibility was confirmed via an MTT assay with HeLa cells. At a pH value of 6, the ND@AuNPs represent a colorimetric probe that can be used to selectively detect the illegally used ß-adrenergic drug clenbuterol (CLB) and the pollutant chromium(III). Detection can be performed visually by monitoring the color change from wine red to purple blue, or by colorimetric measurement of the so-called SPR peaks at 651 and 710 nm. The color changes are due to aggregation, and this is confirmed by TEM and DLS data. The involvement of surface functional groups that assist in analyte recognition was verified by FTIR. The detection limits are 0.49 nM for CLB, and 0.37 nM for Cr(III). The ND@AuNPs were successfully applied to the determination of Cr(III) and CLB in spiked human urine samples. Notably, the low interference by other ions in the detection of Cr(III) in tap and lake water is confirmed by ICP-MS analyses. Graphical abstract Nanodiamonds carrying thiol groups (ND-Thiol) were conjugated to gold nanoparticles, and the resulting ND@AuNPs are shown to be viable probes for the colorimetric detection of sub-nanomolar levels of clenbuterol (CLB) and Cr(III) ions, with demonstrated applicability to real water and urine samples.

A turn-on fluorescent probe for hypochlorous acid based on the oxidation of diphenyl telluride.

A fluorescent probe HCTe was developed for rapid detection of hypochlorous acid based on the specific HOCl-promoted oxidation of diphenyl telluride. The reaction is accompanied by an 82-fold increase in the fluorescence quantum yield (from 0.009 to 0.75). The fluorescence turn-on mechanism is achieved by the suppression of photoinduced electron transfer (PET) from the diphenyl telluride group to BODIPY. The fluorescence intensity of the reaction between HOCl and HCTe is linear in the HOCl concentration range of 1 to 10 µM with a detection limit of 41.3 nM (S/N = 3). In addition, confocal fluorescence microscopy imaging using RAW264.7 macrophages demonstrated that HCTe could be an efficient fluorescent probe for HOCl detection in living cells.

A highly selective turn-on fluorescent sensor for Cu(II) based on an NSe2 chelating moiety and its application in living cell imaging.

In this study, a boron-dipyrromethene (BODIPY)-based fluorescent chemosensor CBS was developed for metal ion sensing. It was found that CBS containing an NSe2 moiety exhibited high selectivity for Cu(2+) detection while CBS in the presence of Cu(2+) displayed significant fluorescence enhancement. However, the metal ions Ag(+), Ca(2+), Co(2+), Cr(3+), Fe(2+), Fe(3+), Hg(2+), K(+), Mg(2+), Mn(2+), Ni(2+), Pb(2+), and Zn(2+) produced only minor changes in the fluorescence values of the system. The binding constant (Ka) of Cu(2+) binding to CBS was found to be 7.28 × 10(3) M(-1). The binding ratio of CBS-Cu(2+) complexes was determined from the Job plot to be 1 : 1. The maximum fluorescence enhancement caused by Cu(2+) binding to CBS was observed over the pH range 5.0-9.0. Additionally, the methyl thiazolyl tetrazolium (MTT) assay demonstrated the CBS to have low cytotoxicity. Confocal fluorescence microscopy imaging using RAW264.7 cells showed that CBS could be used as an effective fluorescent probe for detecting Cu(2+) in living cells.

A pyrene-based highly selective turn-on fluorescent chemosensor for iron(III) ions and its application in living cell imaging.

A new pyrene-based chemosensor (1) exhibits excellent selectivity for Fe(3+) ions over a wide range of tested metal ions Ag(+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(2+), Hg(2+), K(+), Mg(2+), Mn(2+), Ni(2+), Pb(2+), and Zn(2+). The binding of Fe(3+) to chemosensor 1 produces an emission band at 507 nm due to the formation of a Py-Py* excimer that is induced by Fe(3+)-binding. The binding ratio of 1-Fe(3+) was determined to be 1:1 from a Job plot. The association constant of 1-Fe(3+) complexes was found to be 1.27 × 10(4) M(-1) from a Benesi-Hildebrand plot. In addition, fluorescence microscopy experiments show that 1 can be used as a fluorescent probe for detecting Fe(3+) in living cells.

Dual-Responsive Benzo-Hemicyanine-Based Fluorescent Probe for Detection of Cyanide and Hydrogen Sulfide: Real-Time Application in Identification of Food Spoilage.

Colorimetric and fluorescent probes have received a lot of attention for detecting lethal analytes in realistic systems and in living things. Herein, a dual-approachable Benzo-hemicyaninebased red-emitting fluorescent probe PBiSMe, for distinct and instantaneous detection of CN- and HS- was synthesized. The PBiSMe emitted red fluorescence (570 nm) can switch to turn-off (570 nm) and blue fluorescence (465 nm) in response to CN- and HS-, respectively. Other nucleophilic reagents, such as reactive sulfur species (RSS) and anions, have no contact or interference with the probe; instead, a unique approach is undertaken to exclusively interact with CN- and HS- over a wide pH range. The measured detection limits for CN- (0.43 µM) and HS- (0.22 µM) ions are lower than the World Health Organization's (WHO) recommended levels in drinking water. We confirmed 1:1 stoichiometry ratio using Job's plot and observed good quantum yield for both analytes. The probe-coated paper strips were used to detect the H2S gas produced by food spoilage (such as eggs, raw meat, and fish) via an eye-catching visual response. Moreover, fluorescence bioimaging studies of living cells was done to confirm the probe's potential by monitoring the presence of CN- and HS- in a living system.

One-step synthesis of a pH switched pyrene-based fluorescent probe for ratiometric detection of HS- in real water samples.

Only a few probes are suited for highly acidic environments and sensitive to pH values below 4. Thus, finding a solution for detecting strong acidic (pH value below 2) conditions is still challenging. Herein, we constructed and created a pH-switched fluorescent probe based on pyrene and a heteroatom containing pyridine unit. When exposed to acidic environments (pH 2.0), the probe's fluorescence redshifted with distinct colour and fluorescence changes owing to protonation on the nitrogen atom containing pyridine moiety, which could be deprotonated by HS- selectively compared to other competing analytes. Pyr can detect HS- with a rapid response within 5 s and showed very good quantum yield under acidic environments. The sensing mechanism was confirmed by Density Functional Theory (DFT) studies using the B3LYP and 6-31G+ (d) basis sets. Furthermore, the probe was utilized to monitor HS- in actual water samples and identify H2S gas by a simple paper strip test.

Rapid skin biomarker discovery using hydrogel-phase sampling followed by semi-automated liquid-phase re-extraction high-resolution mass spectrometry.

A facile and rapid skin metabolomics protocol is proposed. The liquid microjunction-surface sampling probe system has been partly automated, and used in conjunction with hydrogel probes for skin metabolite analysis. A control device was built to precisely control the segmented solvent flow and analyte re-extraction into the liquid microjunction. This mode provides rapid online re-extraction of the analytes from hydrogel probes. Humectant was added to the hydrogel, and moist heat treatment was used to make the hydrogel probes rugged for sampling in the clinical setting. The developed method was validated for the analysis of choline - a putative biomarker of psoriasis. A linear relationship over six calibration levels from 3.18 × 10-5 to 3.18 × 10-4 mol m-2 has been obtained. The limit of detection was 6.6 × 10-6 mol m-2, while the recoveries range from 92 to 109%. The within-run and between-run precision were evaluated and the coefficients of variation range from 1.84 to 7.13%. Furthermore, the developed method has been used to screen patients (n = 10) and healthy participants (control group; n = 10) for psoriasis-related skin metabolites. Metabolomic profiling of the skin excretion-related signals identified potential biomarkers of psoriasis: choline, pipecolic acid, ornithine, urocanic acid, and methionine.

A BODIPY-based colorimetric and fluorometric chemosensor for Hg(II) ions and its application to living cell imaging.

A new monostyryl boron dipyrromethene derivative (MS1) appended with two triazole units indicates the presence of Hg(2+) among other metal ions with high selectivity by color change and red emission. Upon Hg(2+) binding, the absorption band of MS1 is blue-shifted by 29 nm due to the inhibition of the intramolecular charge transfer from the nitrogen to the BODIPY, resulting in a color change from blue to purple. Significant fluorescence enhancement is observed with MS1 in the presence of Hg(2+); the metal ions Ag(+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(2+), Fe(3+), K(+), Mg(2+), Mn(2+), Ni(2+), Pb(2+), and Zn(2+) cause only minor changes in the fluorescence of the system. The apparent association constant (K(a)) of Hg(2+) binding in MS1 is found to be 1.864 × 10(5) M(-1). In addition, fluorescence microscopy experiments show that MS1 can be used as a fluorescent probe for detecting Hg(2+) in living cells.

A pyrene-based highly selective turn-on fluorescent sensor for copper(II) ion and its application in live cell imaging.

A new pyrene derivative (chemosensor 1) containing a picolinohydrazide moiety exhibits high selectivity for Cu(2+) ion detection in mixed aqueous media (CH(3)OH:H(2)O = 7:3). Significant fluorescence enhancement was observed with chemosensor 1 in the presence of Cu(2+). However, the metal ions Ag(+), Ca(2+), Cd(2+), Co(2+), Cu(2+), Fe(2+), Fe(3+), Hg(2+), K(+), Mg(2+), Mn(2+), Ni(2+), Pb(2+), and Zn(2+) produced only minor changes in fluorescence for the system. The apparent association constant (K(a)) of Cu(2+) binding in chemosensor 1 was found to be 2.75*10(3) M(-1). The maximum fluorescence enhancement caused by Cu(2+) binding in chemosensor 1 was observed over the pH range 5-8. Moreover, by means of fluorescence microscopy experiments, it is demonstrated that 1 can be used as a fluorescent probe for detecting Cu(2+) in living cells.