Highly sensitive and selective detection of triphosgene with a 2-(2'-hydroxyphenyl)benzimidazole derived fluorescent probe.

In this work, a 2-(2'-hydroxyphenyl)benzimidazole derived fluorescent probe, 2-(2'-hydroxy-4'-aminophenyl)benzimidazole (4-AHBI), was synthesized and its fluorescent behavior toward triphosgene were evaluated. The results showed that 4-AHBI exhibited high sensitivity (limit of detection, 0.08 nM) and excellent selectivity for triphosgene over other acyl chlorides including phosgene in CH2Cl2 solution. Moreover, 4-AHBI loaded test strips were prepared for the practical sensing of triphosgene.

A naphthalimide-based and Golgi-targetable fluorescence probe for quantifying hypochlorous acid.

The Golgi apparatus (GA) is a vital organelle in biological systems and excess reactive oxygen species (ROS) is produced during stress in the Golgi apparatus. Hypochlorous acid (HOCl) is a significant reactive oxygen species and has strong oxidative and antibacterial activity, but excessive secretion of hypochlorous acid can affect Golgi structure or function abnormally, it will lead to a series of diseases including Alzheimer's disease, neurodegenerative diseases, autoimmune diseases, and Parkinson's disease. In present work, a novel fluorescent probe for Golgi localization utilizing naphthalimide derivatives was constructed to detect hypochlorous acid. The fluorescent probe used a derivatived 1,8-naphthalimide as the emitting fluorescence group, phenylsulfonamide as the localization group and dimethylthiocarbamate as the sensing unit. When HOCl was absent, the intramolecular charge transfer (ICT) process of the developed probe was hindered and the probe exhibited a weak fluorescence. When HOCl was present, the ICT process occurred and the probe showed strong green fluorescence. When the HOCl concentration was altered from 5.0 × 10-7 to 1.0 × 10-5 mol·L-1, the fluorescence intensity of the probe well linearly correlated with the HOCl concentration. The detection limit of 5.7 × 10-8 mol·L-1 was obtained for HOCl. The HOCl fluorescent probe possessed a rapid reaction time, a high selectivity and a broad working pH scope. In addition, the probe possessed good biocompatibility and had been magnificently employed to image Golgi HOCl in Hela cells. These characteristics of the probe demonstrated its ability to be used for sensing endogenous and exogenous hypochlorous acids within the Golgi apparatus of living cells.

An amino-substituted 2-(2'-hydroxyphenyl)benzimidazole for the fluorescent detection of phosgene based on an ESIPT mechanism.

In this work, an ESIPT-based fluorescence probe, 5'-amino-2-(2'-hydroxyphenyl)benzimidazole (P1), was synthesized and explored for the ratiometric detection of phosgene. Compared to 2-(2'-hydroxyphenyl)benzimidazole (HBI), P1 exhibits high sensitivity (LoD = 5.3 nM) and selectivity toward phosgene with the introduction of the amine group. Furthermore, simple P1 loaded test papers are manufactured and display selective fluorescent detection of phosgene in the gas phase.

A photostable Si-rhodamine-based near-infrared fluorescent probe for monitoring lysosomal pH during heat stroke.

Heat stroke is a symptom of hyperthermia with a temperature of more than 40 °C, which usually leads to all kinds of physical discomfort and even death. It is necessary to study the mechanism of action of heat stroke on cells or organelles (such as cytotoxicity of heat) and the processes of cells or organelles during heat stroke. Recent studies have shown that there is a certain correlation between heat stroke and lysosome acidity. In order to clarify their relationship, Lyso-NIR-pH, a photostable Si-rhodamine-based near-infrared fluorescent probe, was developed for sensing pH changes in lysosomes during heat stroke in this paper. For Lyso-NIR-pH, a morpholine group is employed as the lysosome-targeting unit and a H+-triggered openable deoxylactam is employed as the response unit to pH. Lyso-NIR-pH can detect pH with a high selectivity and a sensitivity, and its pKa is 4.63. Lyso-NIR-pH also has outstanding imaging performances, such as excellent lysosome-targeting ability, low autofluorescence and photostable fluorescence signal, which are in favor of long-term imaging of pH with accurate fluorescence signals. Moreover, we successfully applied Lyso-NIR-pH to monitor lysosomal pH increases induced by chloroquine and apoptosis in live cells. Finally, we successfully applied Lyso-NIR-pH for monitoring changes of lysosomal pH during heat stroke. These results confirmed that Lyso-NIR-pH is a powerful tool to monitor pH change in lysosomes and study its possible effects.

A mitochondria-targetable two-photon fluorescent probe with a far-red to near-infrared emission for sensing hypochlorite in biosystems.

Hypochlorite (ClO-), one of reactive oxygen species (ROS), is closely related with many physiological and pathological processes. Especially as one of cellular reactive oxygen species in mitochondria, ClO- can induce mitochondrial permeability, which leads to apoptosis. Thus, developing an effective method which is able to sense ClO- in mitochondria is important. Although fluorescent probe has become a powerful tool for imaging ClO- in mitochondria, most of them suffered from phototoxicity to biosamples, autofluorescence, and photobleaching phenomenon due to their short-wavelength excitations and emissions. Based on advantages of two-photon fluorescent probe and far-red to NIR fluorescent probe, a mitochondria-targetable two-photon fluorescent probe with a turn-on signal in far-red to NIR region, Mito-TP-ClO, was developed for ClO- in this paper. Mito-TP-ClO is consisted of a triphenylphosphonium cations as a mitochondria-targetable unit and a structure of dibenzoylhydrazine as a response unit to ClO-. Mito-TP-ClO exhibited a high sensitivity and a high selectivity to ClO-, with a linear range from 6.0 × 10-8 to 1.0 × 10-5 M and a detection limit of 2.5 × 10-8 M. Due to its large two-photon cross section (267 GM) and far-red to NIR emission, Mito-TP-ClO exhibits excellent performances including low autofluorescence, photostable fluorescence signal, and deep tissue penetration (230 µM). Moreover, Mito-TP-ClO was successfully used to detect endogenous ClO- in bacteria-infected cells and inflammatory mouse model, which confirmed that Mito-TP-ClO is a powerful tool to monitor ClO- in mitochondria and study on effects of hypochlorite on mitochondria.

A highly selective fluorescent sensor for Fe3+ based on covalently immobilized derivative of naphthalimide.

In this paper, the fabrication and analytical characteristics of fluorescence-based ferric ion-sensing glass slides were described. To fabricate the sensor, a naphthalimide derivative (compound 1) with a terminal double bond was synthesized and copolymerized with 2-hydroxyethyl methacrylate (HEMA) on the activated surface of glass slides by UV irradiation. Upon the addition of Fe(3+) in 0.05 mol/L Tris/HCl (pH 6.02) at 25 °C, the fluorescence intensity of the resulting optical sensor decrease, which has been utilized as the basis for the selective detection of Fe(3+). The sensor can be applied to the quantification of Fe(3+) with a linear range covering form 1.0×10(-5) to 1.0×10(-3) M and a detection limit of 4.5×10(-6) M. The experiment results show that the response behavior of the sensor to Fe(3+) is pH-independent in medium condition (pH 5.00-8.00) and exhibits high selectivity for Fe(3+) over a large number of cations such as alkali, alkaline earth and transitional metal ions. Moreover, satisfactory reproducibility, reversibility and a rapid response were realized. The sensing membrane was found to have a lifetime at least 2 months. The accuracy and the precision of the method were evaluated by the analysis of the standard reference material, iron in water (1.0 mol/L HNO3). The developed sensor is applied for the determination of iron in pharmaceutical preparation samples with satisfactory results.

Graphene oxide-based biosensor for sensitive fluorescence detection of DNA based on exonuclease III-aided signal amplification.

Based on the super fluorescence quenching efficiency of graphene oxide and exonuclease III aided signal amplification, we develop a facile, sensitive, rapid and cost-effective method for DNA detection. In the presence of target DNA, the target-probe hybridization forms a double-stranded structure and exonuclease III catalyzes the stepwise removal of mononucleotides from the blunt 3' termini of probe, resulting in the recycling of the target DNA and signal amplification. Therefore, our proposed sensor exhibits a high sensitivity towards target DNA with a detection limit of 20 pM, which was even lower than previously reported GO-based DNA sensors without enzymatic amplification, and provides a universal sensing platform for sensitive detection of DNA.

(2-Bromo-acet-yl)ferrocene.

In the title mol-ecule, [Fe(C(5)H(5))(C(7)H(6)BrO)], the C atoms of the substituted ring have disparate Fe-C bond lengths compared with the unsubstituted ring. In the bromo-acetyl residue, the Br and O atoms are co-planar [the O-C-C-Br torsion angle is 5.7 (4)°] and are syn to each other. Helical supra-molecular chains along the b axis are formed in the crystal structure mediated by C-H⋯O contacts; the carbonyl-O atom is bifurcated. The chains are linked into layers by C-H⋯π(unsubstituted ring) inter-actions that stack along the a-axis direction.

A highly selective fluorescent sensor for Cu2+ based on a covalently immobilized naphthalimide derivative.

In this paper, we describe the fabrication and analytical characteristics of fluorescence-based copper ion-sensing glass slides. To construct the sensor, a naphthalimide derivative N-allyl-4-(bis(pyridin-2-ylmethyl)amino)ethylamino-1,8-naphthalimide (1) with a terminal double bond was synthesized and photo-copolymerized with 2-hydroxyethyl methacrylate (HEMA) on a glass surface treated with a silanizing agent. In the presence of Cu(2+) at pH 7.24, the resulting optical sensor undergoes fluorescence quenching. Thus, the proposed sensor with visible excitation can behave as a fluorescent sensor for the selective detection of Cu(2+). In addition, the sensor exhibits satisfactory selectivity, reproducibility and response time. The sensing membrane possesses a relatively long lifetime of at least 2 months. The linear response range covers a concentration range of Cu(2+) from 4.0 x 10(-7) to 6.0 x 10(-4) mol/L and the detection limit is 2.0 x 10(-7) mol/L. The determination of Cu(2+) in river water samples shows satisfactory results.

A highly selective fluorescent probe for Hg(2+) based on a rhodamine-coumarin conjugate.

A fluorescent probe 1 for Hg(2+) based on a rhodamine-coumarin conjugate was designed and synthesized. Probe 1 exhibits high sensitivity and selectivity for sensing Hg(2+), and about a 24-fold increase in fluorescence emission intensity is observed upon binding excess Hg(2+) in 50% water/ethanol buffered at pH 7.24. The fluorescence response to Hg(2+) is attributed to the 1:1 complex formation between probe 1 and Hg(2+), which has been utilized as the basis for the selective detection of Hg(2+). Besides, probe 1 was also found to show a reversible dual chromo- and fluorogenic response toward Hg(2+) likely due to the chelation-induced ring opening of rhodamine spirolactam. The analytical performance characteristics of the proposed Hg(2+)-sensitive probe were investigated. The linear response range covers a concentration range of Hg(2+) from 8.0x10(-8) to 1.0x10(-5)molL(-1) and the detection limit is 4.0x10(-8)molL(-1). The determination of Hg(2+) in both tap and river water samples displays satisfactory results.

A ratiometric fluorescent sensor for zinc ions based on covalently immobilized derivative of benzoxazole.

In the present paper, we describe the fabrication and analytical characteristics of fluorescence-based zinc ion-sensing glass slides. To construct the sensor, a benzoxazole derivative 4-benzoxazol-2'-yl-3-hydroxyphenyl allyl ether (1) with a terminal double bond was synthesized and copolymerized with 2-hydroxyethyl methacrylate (HEMA) on the activated surface of glass slides by UV irradiation. In the absence of Zn(2+) at pH 7.24, the resulting optical sensor emitted fluorescence at 450 nm via excited-state intramolecular proton transfer (ESIPT). Upon binding with Zn(2+), the ESIPT process was inhibited resulting in a 46 nm blue-shift of fluorescence emission. Thus, the proposed sensor can behave as a ratiometric fluorescent sensor for the selective detection of Zn(2+). In addition, the sensor shows nice selectivity, good reproducibility and fast response time. Cd(2+) did not interfere with Zn(2+) sensing. The sensing membrane demonstrates a good stability with a lifetime of at least 3 months. The linear response range covers a concentration range of Zn(2+) from 8.0x10(-5) to 4.0x10(-3) mol/L and the detection limit is 4.0x10(-5) mol/L. The determination of Zn(2+) in both tap and river water samples shows satisfactory results.

A fluorescent probe for zinc ions based on N-methyltetraphenylporphine with high selectivity.

N-methyl-alpha,beta,gamma,delta-tetraphenylporphine (NMTPPH) has been used to detect trace amount of zinc ions in ethanol-water solution by fluorescence spectroscopy. The fluorescent probe undergoes a fluorescent emission intensity enhancement upon binding to zinc ions in EtOH/H(2)O (1:1, v/v) solution. The fluorescence enhancement of NMTPPH is attributed to the 1:1 complex formation between NMTPPH and Zn(II) which has been utilized as the basis for the selective detection of Zn(II). The linear response range covers a concentration range of Zn(II) from 5.0x10(-7) to 1.0x10(-5)mol/L and the detection limit is 1.5x10(-7)mol/L. The fluorescent probe exhibits high selectivity over other common metal ions except for Cu(II).

A porphyrin derivative containing 2-(oxymethyl)pyridine units showing unexpected ratiometric fluorescent recognition of Zn2+ with high selectivity.

A porphyrin derivative (1), containing two 2-(oxymethyl)pyridine units has been designed and synthesized as chemosensor for recognition of metal ions. Unlike many common porphyrin derivatives that show response to different heavy metal ions, compound 1 exhibits unexpected ratiometric fluorescence response to Zn(2+) with high selectivity. The response of the novel chemosensor to zinc was based on the porphyrin metallation with cooperating effect of 2-(oxymethyl)pyridine units. The change of fluorescence of 1 was attributed to the formation of an inclusion complex between porphyrin ring and Zn(2+) by 1:1 complex ratio (K=1.04x10(5)), which has been utilized as the basis of the fabrication of the Zn(2+)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Zn(2+)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Zn(2+) with a linear range covering from 3.2x10(-7) to 1.8x10(-4) M and a detection limit of 5.5x10(-8) M. The experiment results show that the response behavior of 1 to Zn(2+) is pH-independent in medium condition (pH 4.0-8.0) and show excellent selectivity for Zn(2+) over transition metal cations.