Boosting Photon Emission from the Chemiluminescence of Luminol Based on Host-Guest Recognition for the Determination of Dopamine.

Modulating the photon emission of the luminophore for boosting chemiluminescence (CL) response is very crucial for the construction of highly sensitive sensors via the introduction of functionalized materials. Herein, the integration of the emitter and coreactant accelerator into one entity is realized by simply assembling cucurbit[7]uril (CB[7]) on the surface of gold nanoparticles (AuNPs) through simple assembly via a Au-O bond. The loaded CB[7] on the AuNPs improves their catalytic capacity for the generation of hydroxyl radicals(•OH). Moreover, the host-guest recognition interaction between luminol and CB[7] enables the capture of luminol on AuNPs efficiently. Also, the intramolecular electron-transfer reaction between the luminol and •OH enables the CL response more effectively in the entity, which greatly boosts photon emission ca 100 folds compared with the individual luminol/H2O2. The host-guest recognition between luminol and CB[7] is revealed by Fourier transform infrared spectroscopy, electrochemical, and thermogravimetric characterization. Moreover, the proposed CL system is successfully used for the sensitive and selective determination of dopamine (DA) based on a synergistic quenching mechanism including the competition quenching and radical-scavenging effect from DA. The present amplified strategy by integrating recognized and amplified elements within one entity simplifies the sensing process and holds great potential for sensitive analysis based on the self-enhanced strategies.

Interaction between Phthalate Ester and Rice Plants: Novel Transformation Pathways and Metabolic-Network Perturbations.

Our understanding is limited concerning the interaction mechanism between widespread phthalate esters and staple crops, which have strong implications for human exposure. Therefore, this study was aimed at illuminating the transformation pathways of di-n-butyl phthalate (DnBP) in rice using an untargeted screening method. UPLC-QTOF-MS identified 16 intermediate transformation products formed through hydroxylation, hydrolysis, and oxidation in phase I metabolism and further by conjugation with amino acids, glutathione, and carbohydrates in phase II metabolism. Mono-2-hydroxy-n-butyl phthalate-l-aspartic acid (MHBP-asp) and mono-2-hydroxy-n-butyl phthalate-d-alanyl-ß-d-glucoside (MHBP-ala-glu) products were observed for the first time. The proteomic analysis demonstrated that DnBP upregulated the expression of rice proteins associated with transporter activity, antioxidant synthesis, and oxidative stress response and downregulated that of proteins involved in photosynthesis, photorespiration, chlorophyll binding, and mono-oxygenase activity. Molecular docking revealed that DnBP can affect protein molecular activity via pi-sigma, pi-alkyl, and pi-pi interactions or by forming carbon-hydrogen bonds. The metabolomic analysis showed that key metabolic pathways including citrate cycle, biosynthesis of aminoacyl-tRNA, and metabolism of amino acids, sphingolipids, carbohydrates, nucleotides, and glutathione were activated in rice plants exposed to DnBP and its primary metabolite mono-n-butyl phthalate (MnBP). Furthermore, exposure to 80 ng/mL MnBP significantly perturbed the metabolic profile and molecular function in plants, with downregulation of the levels of beta-alanine (0.56-fold), cytosine (0.48-fold), thymine (0.62-fold), uracil (0.48-fold), glucose (0.59-fold), and glucose-1-phosphate (0.33-fold), as well as upregulation of the levels of l-glutamic acid (2.97-fold), l-cystine (2.69-fold), and phytosphingosine (38.38-fold). Therefore, the degradation intermediates of DnBP pose a potentially risk to plant metabolism and raise concerns for crop safety related to plasticizer pollution.

Facile Uniaxial Electrospinning Strategy To Embed CsPbBr3 Nanocrystals with Enhanced Water/Thermal Stabilities for Reversible Fluorescence Switches.

All-inorganic halide perovskite nanocrystals with their fascinating optical properties have drawn increasing attention as promising nanoemitters. However, due to the intrinsic poor colloidal stability against the external environment, the practical applications are greatly limited. Herein, a facile and effective strategy for the in situ encapsulation of CsPbBr3 NCs into highly dense multichannel polyacrylonitrile (PAN) nanofibers via a uniaxial electrospinning strategy is presented. Such a facile uniaxial electrospinning strategy enables the in situ formation of CsPbBr3 NCs in PAN nanofibers without the introduction of stabilizers. Significantly, the obtained CsPbBr3 nanofibers not only display intense fluorescence with a high quantum yield (≈48%) but also present high stability when exposed to water and air owing to the peripheral protecting matrix of PAN. After immersing CsPbBr3@PAN nanofiber films in water for 100 days, the quantum yield of CsPbBr3@PAN nanofibers maintained 87.5% of the original value, which was much higher than that using CsPbBr3 NCs. Furthermore, based on the spectral overlap between the electrochromic material of ruthenium purple and fluorescence of CsPbBr3@PAN nanofiber films with excellent water stability, a reversible fluorescence switch is constructed with good fatigue resistance, suggesting their promising applications.

Atom-Anchoring Strategy with Metal-Organic Frameworks for Highly Efficient Solid-State Electrochemiluminescence.

A chemical fixation strategy originating from single-atom-anchoring with metal-organic frameworks as a carrying matrix was proposed for solid-state electrochemiluminescence (ECL). Herein, UiO-67(N) with the exposure of 2,2'-bipyridine (bpy) ligands could coordinate with Ru2+ to form a local structure of [Ru(bpy)3]2+ (Ru-UiO). The influence of the steric effect induced with different Ru sources was discussed. The as-obtained Ru-UiO exhibits high ECL intensity and outstanding stability in the presence of a coreactant at low concentrations. The proposed synthesis strategy may hold great potential for the synthesis of solid-state ECL materials and their further utilization in ECL analysis.

Catalytical feature of optical nanoprobes of boron nitride quantum dots in the presence of Cu2+ for the determination of dopamine.

Monitoring the concentration of dopamine (DA) is vital for preventing and diagnosing DA related diseases. In contrast to the traditional sensing methods for DA, in which direct or indirect effects on the optical probes are often recorded, a novel sensing concept is disclosed based on as a result of the in situ formation of polydopamine (PDA) originating from the synergetic effect between boron nitride quantum dots (BNQDs) and Cu2+. In the co-presence of BNQDs and Cu2+, DA was catalytically oxidized to PDA, accompanied by an obvious color change from colorless to brown. In contrast to previous reports, in which BNQDs have been employed as an optical probe, herein, the BNQDs not only acted as the optical energy donor, but also as the catalysts for the formation of PDA. The quenching efficiency resulting from the inner filter effect and the electron transfer between the BNQDs and PDA was directly proportional to the concentration of DA, ranging linearly from 2 to 80 µM with a limit of detection of 0.49 µM. The present system exhibited an outstanding selectivity for DA among other interfering coexisting biomolecules. Furthermore, the practical application of the proposed platform was verified by assaying DA in human plasma samples, and satisfactory recoveries ranging from 101.24% to 111.98% were obtained. With the satisfactory reliability, repeatability and stability, the proposed simple sensor showed significant potential for use in DA detection in other biomedical applications.

Universal Platform for Ratiometric Sensing Based on Catalytically Induced Inner-Filter Effect by Cu2.

Integrating two kinds of fluorescent probes in one system to develop a ratiometric sensing platform is of prime importance for achieving an accurate assay. Inspired by the efficient overlapped spectrum of 2-aminoterephthalic acid (PTA-NH2) and 2,3-diaminophenazine (DAP), a new sensitive ratiometric fluorescent sensor has been developed for Cu2+ on the basis of in situ converting o-phenylenediamine (OPD) into DAP through the catalysis of Cu2+. Here, the presence of Cu2+ induced the emission of DAP, which acted as an energy acceptor to inhibit the emission of PTA-NH2. This dual-emission reverse change ratiometric profile based on the inner-filter effect improved sensitivity and accuracy, and the highly sensitive determination of Cu2+ with a detection limit of 1.7 nmol·L-1 was obtained. The proposed sensing platform displayed the wide range of detection of Cu2+ from 5 to 200 nmol·L-1 by modulating the reaction time between Cu2+ and OPD. Moreover, based on the specific interaction between glutathione (GSH) and Cu2+, this fluorescent sensor showed high response toward GSH in a range of 0.5-80 µmol·L-1 with a detection limit of 0.16 µmol·L-1. The successful construction of this simple ratiometric sensing platform without the participation of enzymes provides a new route for the detection of small biological molecules that are closely related to human health.

In Situ Formed Catalytic Interface for Boosting Chemiluminescence.

Designing the catalytic interface that preferentially attracts reactants is highly desirable for amplifying chemiluminescence (CL) emission. Herein, to boost the generation of reactive oxygen species (ROS) from dissolved O2 molecule, flower-like cobalt hydroxide (f-Co(OH)2) based catalytic interface with hierarchical and porous architecture were in situ created in the coexistence of BSA and Co2+. Benefiting from the oxidase-like catalysis capability and the unique microstructure of f-Co(OH)2, ROS was efficiently produced. Meanwhile, the capping ligands of BSA endowed the interface with the capability of enriching functionality through the interaction between BSA and luminol. 100-fold CL enhancement was achieved using the as-prepared catalytic interface compared with the classical luminol-Co2+ or luminol-BSA system. Moreover, the proposed catalytic amplification mechanism could be extended to the different proteins such as lysozyme, protamine, thrombin, papain. Based on the quenching effect on CL, a sensitive sensing platform was constructed for the determination of ascorbic acid with satisfied results. Our finding provided a novel "all-in-one" route to design the catalytic interface for amplifying CL emission.

Glutathione Regulated Inner Filter Effect of MnO2 Nanosheets on Boron Nitride Quantum Dots for Sensitive Assay.

Glutathione (GSH) can help the body maintain the function of the normal immune system and its level change is associated with a variety of diseases. To achieve the ultrasensitive assay of GSH, a "switch on" nanosensor is designed on the basis of GSH regulating the inner filter effect (IFE) of MnO2 nanosheets (MnO2 NS) on boron nitride quantum dots (BNQDs). Here, the fluorescence of BNQDs is quenched efficiently in the presence of redoxable MnO2 NS because of the superior light absorption capability; however, the introduction of GSH can trigger the decomposition of MnO2 to Mn2+ and weaken the IFE, causing the partial fluorescence recovery. The recovered fluorescence is dependent on the concentration of GSH. Under the optimal conditions, this sensing platform shows the response to GSH in the range of 0.5-250 µM with the detection limit of 160 nM. On the basis of the GSH activated reduction of MnO2 NS, the MnO2 NS/BNQDs nanoprobes exhibit good selectivity to GSH. The practical application of the proposed system is demonstrated by detecting the GSH in human plasma samples with satisfying results.

Boron Nitride Quantum Dots as Efficient Coreactant for Enhanced Electrochemiluminescence of Ruthenium(II) Tris(2,2'-bipyridyl).

In the present work, an enhanced and stable anodic electrochemiluminescence (ECL) was observed from a suspension of boron nitride quantum dots (BNQDs) and Ru(bpy)32+, which had a 400-fold enhancement compared with individual Ru(bpy)32+. Interestingly, different from the previous research on BNQDs as a type of optical probe, BNQDs were demonstrated as an efficient coreactant of Ru(bpy)32+-based ECL for the first time and confirmed by collecting the ECL spectra. The amino-bearing groups and the electrocatalytic effect of the BNQDs endowed them as potential coreactants for ECL of Ru(bpy)32+, and the possible mechanism of the electrode surface reaction was discussed. Several factors including electrode material, the pH of the buffer solution, and the amount of BNQDs were investigated and also further confirmed the role of the BNQDs in the proposed Ru(bpy)32+/BNQDs system. On the basis of the quenching effect between the excited state of Ru(bpy)32+ and the oxidation form of DA in the ECL system of Ru(bpy)32+/BNQDs, the ECL sensing platform for DA was successfully established. The proposed ECL system with the outstanding ECL efficiency may hold great potential in the bioanlysis because of the biocompatibility and good stability of BNQDs.

Point-of-Care Diagnoses: Flexible Patterning Technique for Self-Powered Wearable Sensors.

This paper demonstrated the fabrication of a facile, low-cost, and self-powered platform for point-of-care fitness level and athletic performance monitoring sensor using electrochemical lithography method and its application in body fluid sensing. Flexible Au/prussian blue electrode was employed as the indicating electrode, where the color change was an indication of fitness level and athletic performance. A piece of Al foil, Au/multiwalled carbon nanotubes (MWCNTs)-glucose dehydrogenase, and Au/polymethylene blue-MWCNTs-lactic dehydrogenase electrodes were used for the detection of ionic strength, glucose, and lactic acid in sweat, respectively, which allows the sensor to work without any extra instrumentation and the output signal can be recognized by the naked eyes. The advantages of these sensors are (1) self-powered; (2) readily applicable to the detection of any electroactive substance by an electrochromic material; (3) easy to fabricate via two steps of EDP; and (4) point-of-care. By assembling the energy and sensing components together through a transparent adhesive tape, the proposed self-powered wearable biosensor exhibits superior performances, indicating its broad applied prospect in the point-of-care diagnoses.

Chemiluminescence of CsPbBr3 Perovskite Nanocrystal on the Hexane/Water Interface.

All-inorganic halide perovskite CsPbBr3 nanocrystals (NCs) have attracted more attention in recent years due to the unique optical feature. To date, most of the research was mainly focused on the photoluminescence (PL) and electrochemiluminescence (ECL) of the perovskite NCs. In this work, the strong chemiluminescence (CL) emission of CsPbBr3 NCs was observed for the first time on the hexane/water interface with the assistance of ammonium persulfate-(NH4)2S2O8 as coreactant. Different coreactants were investigated to demonstrate the effect on the CL behavior and it was found that CL intensity achieved the maximum in the presence of (NH4)2S2O8. In this system, electron transfer took place on the surface of the CsPbBr3 NCs, and the excited CsPbBr3 NCs was originated from the direct chemical oxidation of (NH4)2S2O8. The CL spectrum of CsPbBr3 NCs was also collected and was consistent with their PL and ECL spectra, indicating that CsPbBr3 NCs played a role of luminophor during the CL process. The discovery of monochromatic CL of highly crystallized CsPbBr3 NCs not only extends the applications of halide perovskite materials in the analytical field but also provides a new route for the exploration of the physical chemistry properties.

Enhanced Electrochemiluminescence Behavior of Gold-Silver Bimetallic Nanoclusters and Its Sensing Application for Mercury(II).

Bimetallic nanoclusters (NCs) with superior performance to that of monometallic nanoclusters have attracted extensive research interest due to the synergetic effect of the two atoms. Inspired from the silver effect on the enhanced fluorescence intensity of Au NCs, a series of bovine serum albumin-protected Au-Ag bimetallic NCs were prepared by regulating the molar ratios of HAuCl4/AgNO3 and their electrochemiluminescence (ECL) property was investigated using triethylamine as co-reactant. Notably, multifold higher efficiency was achieved with Au-Ag bimetallic NCs in reference to the monometallic nanoclusters. Moreover, the doping of Ag atoms not only made the ECL emission of the Au NCs blue shift but also decreased the peak potential and onset potential, which provided an efficient and facile way to improve the ECL behavior. Based on the ECL quenching effect of Hg2+ toward Au-Ag bimetallic NCs via the formation of metallophilic bond, an ECL sensor for Hg2+ detection was proposed with good stability and high selectivity and sensitivity. These results indicated that the as-prepared Au-Ag bimetallic NCs with enhanced ECL properties can be served as an ideal luminescent material in sensing application.

Bipolar Electrode Based Reversible Fluorescence Switch Using Prussian Blue/Au Nanoclusters Nanocomposite Film.

A highly efficient fluorescence switch system based on a closed bipolar electrode (C-BPE) system was proposed for the first time. Here, Au nanoclusters (Au NCs) were premodified on one pole of the BPE and acted as the fluorescent donor. On the basis of the spectral overlap between the absorbance of electrochromic material-Prussian blue (PB) and the fluorescence spectrum of Au NCs, fluorescence quenching ("off" state) induced by the inner filter effect was observed. Due to the electrochemical reversible redox reaction between PB and Prussian white, switching the polarity of driving voltage could easily achieve the fluorescence recovery of the Au NCs, corresponding to the "on" state. Through the reasonable design of C-BPE and optimization of driving voltage, the on-off ratio of the integrated fluorescence switch was up to 2.7 and a good fatigue resistance while performing 10 on-off cycles was obtained owing to the good stability of Au NCs and the reversible redox feature of PB. The introduction of BPE made the fluorescence switch more simple and controllable compared with the traditional three-electrode system, which will provide a new route for the design of the electrical-stimuli responsive fluorescence switch, especially for the integration of the miniaturized device.

Three new anthraquinones from the twigs of Cassia fistula and their bioactivities.

Three previously unreported anthraquinones, fistulaquinones A-C (1-3), together with three known ones (4-6) were isolated from the twigs of Cassia fistula. Their structures were determined by means of extensive NMR and MS spectroscopic analyses. All the isolated compounds were tested for their anti-tobacco mosaic virus (anti-TMV) activity, and compound 3 showed significant activity with inhibition rate of 34.5% at 20 µM concentration, even more potent than positive control. Additionally, compounds 1-6 exhibited moderate cytotoxicity with IC50 values ranging from 2.8 to 9.4 µM for some tested human tumor cell lines.

[A new cytotoxic alkaloid from roots of Alangium chinense].

We have carried out the chemical investigation on the roots of Alangium chinense. The chemical constituents from the roots of A.chinense were isolated and purified by various chromatographic techniques, such as silica gel, MCI-Gel resin, Sephadex LH-20 and high performance liquid chromatography. As a result, three alkaloids (1-3) were isolated from 90% EtOH extracts of the roots of this plant. Their structures were elucidated by physical-chemical properties and spectral data. Among them, compound 1 is a new compound, determined as 8-hydroxy-3-hydroxymethyl-6,9-dimethyl-7H-benzo[de]isoquinolin-7-one. Cytotoxicity of the compounds was evaluated by the MTT method. Compound 1 displayed cytotoxicity against NB4, A-549, SHSY5Y, PC-3 and MCF-7 cell lines with IC50 values of 4.2, 3.5, 5.7, 2.8 and 3.9 µmol•L⁻¹, respectively.

Three new biphenyls from the twigs of Garcinia tetralata and their anti-tobacco mosaic virus activity.

Phytochemical investigations on the ethanol extract of the twigs of Garcinia tetralata resulted in the isolation of three new biphenyls, tetralatabiphenyls A-C (1-3), along with three known biphenyl derivatives (4-6). Structural elucidations of 1-3 were performed by spectroscopic methods such as 1D and 2D NMR spectra, in addition to high-resolution mass spectra. Compounds 1-6 were also evaluated for their anti-tobacco mosaic virus (anti-TMV) activity. The results showed that compound 3 showed high anti-TMV activity with inhibition rate of 31.1%. Compounds 1, 2, and 4-6 also showed modest anti-TMV activities with inhibition rates in the range of 18.9-24.5%, respectively.

[A new furan-2-carboxylic acid from stem bark of Cassia alata].

A new furan-2-carboxylic acid, 5-[3-(hydroxymethyl)-4,5-dimethoxyphenyl]-3-methylfuran-2-carboxylic acid(1),has been isolated from the bark of Cassia alata by using various chromatographic techniques. It displayed cytotoxicity against NB4, A549, SHSY5Y, PC3 and MCF7 cell lines with IC50 values of 2.5, 1.2, 2.2, 3.6 and 1.9 µmol•L⁻¹, respectively.

[A new sesquiterpene from seeds of Cassia occidentalis and its cytotoxicity].

For the purpose of finding new bioactive agents from ethnic medicines, the chemical study on Dai Medicine Cassia occidentalis was carried out. The chemical constituents from the seeds of C. occidentalis were isolated by column chromatographic methods on silica gel, MCI-Gel resin, Sephadex LH-20, and high performance liquid chromatography. Their structures were elucidated by spectroscopic methods, including extensive 1D and 2D NMR techniques. The cytotoxicity of the compound for NB4, A549, SHSY5Y, PC3, and MCF7 cells line was also assayed by using the MTT method. Two sesquiterpenes (1 and 2) were isolated from this plant. Compound 1 is a new compound and named as methyl 6-(hydroxymethyl)-4-isopropyl-7-methoxynaphthalene-1-carboxylate. Compound 1 also displayed high cytotoxicity with the tested cancer cell-lines.

[A new nor-sesquiterpene from Cassia occidentalis and its bioactivity].

The phytochemistry investigation on the Cassia occidentalis, a Dai Medicine, was carried out. The C. occidentalis was extracted with ethanol and then partitioned with EtOAc. The EtOAc soluble materials were subjected repeatedly to column chromatography on silica gel and preparative RP-HPLC, leading to isolation of a nor-sesquiterpene, 3-isopropyl-1,6-dimethoxy-5-methyl-naphthalen-7-ol (1), and a sesquiterpene, 2,7-dihydroxy-4-isopropyl-6-methyl-naphthalene-1-carbaldehyde (2). Their structures were determined by means of spectroscopic studies. Compound 1 is a new compound. Compound 2 is also isolated from C. occidentalis for the first time. In addition, the cytotoxicity of compound 1 for NB4, A549, SHSY5Y, PC3, and MCF7 cells line was assayed by using the MTT method, and it displayed potential cytotoxicity for the tested cancer cell-line with IC50 valves of (1.8±0.2), (1.2±0.2), (0.9±0.1), (2.2±0.3), (2.6±0.3) µmol•L⁻¹, respectively.

[A new isoindole alkaloid from leaves of Cassia siamea].

A new isoindole alkaloid (1), has been isolated from the leaves of Cassia siamea by using various chromatographic techniques. Compound 1 is a new compound, determined as 5-(hydroxymethyl)-2-methyl-6-prenylisoindolin-1-one, and it displayed cytotoxicity against NB4, A549, SHSY5Y, PC3 and MCF7 cell lines with IC50 values of 3.2,4.6,2.8,6.4, 2.5 µmol•L⁻¹, respectively.