A magnetically induced self-assembly of Ru@Fe3O4/rGO cathode for diclofenac degradation in electro-Fenton process.

In this study, a novel magnetic nanocomposite of Ru@Fe3O4/rGO was successfully synthesized by a simple hydro-thermal method. The Ru@Fe3O4/rGO particles were assembled and immobilized for innovative magnetically assembled electrode (MAE) without any binder, and the electrode was further applied in heterogeneous electro-Fenton (hetero-EF) process for the degradation of diclofenac (DCF). The results showed that rGO could remarkably enhance the conductivity and catalyze the two-electron oxygen reduction, which greatly improved the generation of H2O2. In addition, the mixture valence of Fe and Ru species might provide rich reaction sites and enhance electron transfer by synergy. Thus, the Ru@Fe3O4/rGO MAE exhibited a stable and high electrocatalytic activity in the hetero-EF process for DCF degradation over a wide pH range from 2 to 9 owing to the higher electroactive surface area (EASA) and lower charge/mass-transfer resistance. The DCF degradation efficiency could reach about 100% within 90 min under pH 5 and current 40 mA, and the Ru@Fe3O4/rGO MAE showed high stability and reusability after five cycles. Theoretically, 1O2 and •OH were the main reactive oxygen species (ROS) participating in DCF degradation in the Ru@Fe3O4/rGO MAE hetero-EF process. Furthermore, according to the LC-MS/MS intermediates, the possible DCF degradation pathway was deduced including dechlorination, hydroxylation and ring opening attacked by ROS. Eleven intermediates were detected during DCF degradation in the MAE hetero-EF process, and the ecological risk of DCF degradation in Ru@Fe3O4/rGO MAE hetero-EF process was significantly reduced. This study provides new insights into the magnetically assembled electrode of Ru@Fe3O4/rGO and displays a new practical application prospect of the materials for high-efficient removal and degradation of DCF from wastewater.

Machine Learning Algorithms for Intelligent Decision Recognition and Quantification of Cr(III) in Chromium Speciation.

Cr(III) is a common oxidation state of chromium, and its presence in the environment can occur naturally or as a result of human activities, such as industrial processes, mining, and waste disposal. This article explores the application of machine learning algorithms for the intelligent decision recognition and quantification of Cr(III) in chromium speciation. Three different machine learning models, namely, the Decision Tree (DT) model, the PCA-SVM (Principal Component Analysis-Support Vector Machine) model, and the LDA (Linear Discriminant Analysis) model, were employed and evaluated for accurate and efficient classification of chromium concentrations based on their fluorescence responses. Furthermore, stepwise multiple linear regression analysis was utilized to achieve a more precise quantification of trivalent chromium concentrations through fluorescence visualization. The results demonstrate the potential of machine learning algorithms in accurately detecting and quantifying Cr(III) in chromium speciation with implications for environmental and industrial applications in chromium detection and quantification. The findings from this research pave the way for further exploration and implementation of these models in real-world scenarios, offering valuable insights into various environmental and industrial contexts.

Dual-responsive ratiometric fluorescent sensor for tetracyclines detection based on europium-decorated copper nanoclusters.

Development of accurate and efficient TCs residue analysis methods is of great significance for the protection of environment, food safety and public health. Herein, a dual-responsive ratiometric fluorescence sensor being capable of simple and sensitive detection of tetracycline (TC) was presented, which was constructed by immobilizing europium ions (Eu3+) onto the mercaptopropionic acid stabilized copper nanoclusters (MPA-Cu NCs). In the presence of TC, the red fluorescence of Eu3+ was enhanced through antenna effect (AE), while the green fluorescence of MPA-Cu NCs was quenched through internal filter effect (IFE), leading to an obvious fluorescence color evolution from green to red for the probe solution. In addition to successful design of a smartphone-assisted colorimetric analysis platform for portable detection, a logic gate device capable of intelligently monitoring TC concentration is also designed.

Europium-modified carbon nitride nanosheets for smartphone-based fluorescence sensitive recognition of anthrax biomarker dipicolinic acid.

Development of selective and sensitive methods for the detection of 2, 6-dipicolinic acid (DPA), a biomarker produced by bacterial spores, is of great significance for maintaining public health and food safety. Herein, a ratiometric fluorescence strategy using graphene carbon nitride (g-C3N4) coupled with Eu3+ is designed for the assay of DPA. As the concentration of DPA increases, the emission intensity of g-C3N4 kept constant which acted as a stable internal reference, while the fluorescence of Eu3+ was enhanced obviously due to the antenna effect. The linear calibration ranged from 0.1 to 15 µM with a detection limit of 13 nM was obtained. More Importantly, a paper-based sensor with a smartphone was successfully combined to perform colorimetric and visual detection of DPA in situ. This method has good performance for the detection of DPA, which is expected to broaden the application prospects of preliminary biomarker monitoring.

Highly selective and sensitive determination of ceftriaxone sodium using nitrogen-rich carbon dots based on ratiometric fluorescence.

Selective and sensitive determination of ceftriaxone sodium (CTR) trace residues is of great importance for food safety and environmental protection. Herein, a determination method based on ratiometric fluorescence and colorimetric method with nitrogen-rich carbon dots as fluorophore is reported. The functional surfaces of indole-derived carbon dots (I-CDs) containing nitrogen and carbon groups can be selectively bound to CTR by electrostatic forces, leading to a hindered conjugation system and deprotonation of the amine on the pyrrole ring, resulting in a distinct variety in fluorescence and absorption wavelength and intensity. With the addition of CTR, the fluorescence at 577 nm can be selectively quenched, accompanied by a new emission peak appeared at 507 nm. The limits of detection (LODs) were estimated to be 19.7 nM and 78.0 nM based on the ratiometric fluorescence method and colorimetric method, respectively. Finally, the in situ visual quantitative determination of CTR using this nanosensor was achieved by combining with the color recognizer of a smartphone, and the method was further validated by spike and recovery test in real water samples including milk, seawater, and tap water.

Oxygen mediated oxidative couplings of flavones in alkaline water.

Catalyzed oxidative C-C bond coupling reactions play an important role in the chemical synthesis of complex natural products of medicinal importance. However, the poor functional group tolerance renders them unfit for the synthesis of naturally occurring polyphenolic flavones. We find that molecular oxygen in alkaline water acts as a hydrogen atom acceptor and oxidant in catalyst-free (without added catalyst) oxidative coupling of luteolin and other flavones. By this facile method, we achieve the synthesis of a small collection of flavone dimers and trimers including naturally occurring dicranolomin, philonotisflavone, dehydrohegoflavone, distichumtriluteolin, and cyclodistichumtriluteolin. Mechanistic studies using both experimental and computational chemistry uncover the underlying reasons for optimal pH, oxygen availability, and counter-cations that define the success of the reaction. We expect our reaction opens up a green and sustainable way to synthesize flavonoid dimers and oligomers using the readily available monomeric flavonoids isolated from biomass and exploiting their use for health care products and treatment of diseases.

A reusable ratiometric fluorescent probe for the detection and removal of doxycycline antibiotic demonstrated by environmental sample investigations.

Tetracycline antibiotic residues have attracted worldwide attention due to the serious damage to human health and the environment. However, most of the reported fluorescent probes were based on a single fluorescence channel-based response, which often suffered from signal fluctuation-induced poor reproducibility. Herein, by taking advantage of the unique properties of zeolitic imidazolate frameworks (ZIFs), a novel europium-doped ZIF nanocomposite (ZIF-Eu) was reported for the detection of doxycycline (DOX) in a ratiometric fluorescence manner. The synthesized probe only showed blue fluorescence at 420 nm since the fluorescence of Eu was quenched by the coordinated water molecules. However, due to the strong coordination ability of DOX to Eu atoms, the probe solution demonstrated an obvious fluorescence enhancement at 615 nm in the presence of DOX, while the blue fluorescence signal remained unchanged, realizing a ratiometric fluorescence response to DOX with a good linear range from 1 to 9 µM and a detection limit of 49 nM. Interestingly, it is found that DOX could be discriminated from other tetracycline antibiotics using this ratiometric fluorescent probe. In addition, direct detection of DOX in soil samples, the DOX removal efficiency and the reusability of the proposed ZIF-Eu nanocomposite were demonstrated to evaluate its potential in environmental remediation application.

Methyl position affect the fluorescence performance of HBT derivatives for the detection of hypochlorite under alkaline condition.

Five fluorescent derivatives of hydroxyphenyl-benzothiazole (HBT) with different methyl positions at the hydroxyphenyl group were synthesized with good yield. Their reactivity and fluorescent response to hypochlorite were carefully studied. It was found that the HBT derivatives with meta-methyl (3-HBT or 5-HBT) showed the highest reactivity to hypochlorite under basic conditions, accompanied by the most efficient fluorescence quenching, whereas HBT derivatives with ortho or para methyl exhibited the least reactivity to hypochlorite. The LUMO and HOMO of 3-HBT were further verified to explain the fluorescence behavior by density functional theory (DFT) calculation. The excellent selectivity of 3-HBT toward hypochlorite against other reactive oxygen species (ROS) was also evaluated under the same conditions. The compounds emit bright green fluorescence in a solid-state, which is convenient for designing sensing devices for hypochlorite in water samples. Thus, the HBT derivatives with meta methyl (3-HBT) were successfully applied to fabricate paper sensors for the quantification of hypochlorite in tap water. Hence, the fluorescent 3-HBT exhibits great promise as a selective and sensitive hypochlorite probe in chemical and biological applications.

Three-Dimensional Quantitative Structure and Activity Relationship of Flavones on Their Hypochlorite Scavenging Capacity.

Flavonoids, a class of polyphenolic substances widely present in the plant realm, are considered as ideal hypochlorite scavengers. However, to our knowledge, little study has focused on the structure-activity relationship between flavonoids and hypochlorite scavenging capacity. Herein, we report for the first time the three-dimensional quantitative structure and activity relationship (3D-QSAR) combined with comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA). Four models derived from CoMFA and CoMSIA with different combinations of descriptors were built and compared; the CoMFA model, which included both steric and electrostatic fields, showed great potential (R2 = 0.989; Q2 = 0.818) in predictive quality according to both internal and external validation criteria. Additionally, the average local ionization energy (ALIE), electrostatic potential (ESP), and orbital weighted dual descriptor (OWDD) were determined to identify the key structural moiety for scavenging capacity of flavonoids against hypochlorite. The computational results indicated that hypochlorous acid (HClO) serves as an electrophile undergoing electrophilic addition to the C6 carbon, which has the highest negative charge density, which are influenced by the functional groups on the flavones. The DFT calculated mechanism revealed the catalytic role of water of mono- and di-chlorination reactions, characterized by low activation barriers, and the involvement of neutral, instead of high-energy carbocation, intermediates.

Multi-dentate chelation induces fluorescence enhancement of pyrene moiety for highly selective detection of Fe(III).

Fluorescence enhancement has great advantages and various promising applications for a fluorescent molecular probe, which shows high sensitivity and high selectivity. In this report, a novel pyrene-based fluorescent probe with multidentate ligand (PPD) was synthesized for highly selective detection of Fe(III), which exhibited great fluorescence enhancement response upon the addition of Fe(III) in aqueous solution of pH 3.5 ~ 7.5, with a detection limit of 115 nM. The probe also has good water solubility and photostability. Further fluorescence titration confirmed 1:1 stoichiometric ratio for the probe PPD-Fe(III), which can be applied for quantification of Fe(III). The probe was validated for ferric detection in real water samples by spike and recovery test.

In situ low-temperature pyrolysis fabrication type II BiOIO3/Bi4O5I2 heterostructures with enhanced visible-light-driven photooxidation activity.

Novel visible-light-driven heterostructure semiconductors are considered as promising photocatalysts for the elimination of environmental organic pollutants. Herein, a solvent-assisted low-temperature in situ calcination strategy was developed to fabricate type II BiOIO3/Bi4O5I2 heterojunction by using BiOIO3 as self-sacrificed template. The phase transition temperature of BiOIO3 was reduced under solvent-assisted operating conditions. By controlling the elevated temperature from 200 to 300 °C, an in situ stepwise pyrolysis reaction occurred during the calcination process, which was described as BiOIO3 → BiOIO3/Bi4O5I2 → Bi4O5I2. The light absorption edge of different samples significantly red shifted from 385 to 632 nm with the increase of calcination temperature. Meanwhile, two interlocked interface lattice fringes were identified in high resolution transmission electron microscope (HRTEM) of BiOIO3/Bi4O5I2-250 composites, confirming the formation of BiOIO3/Bi4O5I2 heterojunction. The as-obtained BiOIO3/Bi4O5I2 heterojunction demonstrated the optimal photodegradation performance, which brought about 99.4% of bisphenol A (BPA) degraded within 30 min visible light (λ > 420 nm) illumination. Besides, after 5 repeated cycles, the photoactivity of BiOIO3/Bi4O5I2 heterojunction still maintained 91.5%, unfolding its high photostability. The superior photoreactivity of BiOIO3/Bi4O5I2 nanosheets was assigned to the formation of well-matched type II heterojunction, which significantly enhanced the separation and migration of photoinduced charge carriers. Superoxide radical (O2-) and hole (h+) are dominant reactive species in this photodegradation system. Based on active species quenching experiments and electron paramagnetic resonance (ESR) measurements, a possible type II heterojunction mechanism for enhanced photodegradation performance of BiOIO3/Bi4O5I2 heterostructure was proposed. This work affords an innovative method for design and construction of type II composites toward sustainable water purification.

Quantitative Determination of Ethylene Using a Smartphone-Based Optical Fiber Sensor (SOFS) Coupled with Pyrene-Tagged Grubbs Catalyst.

For rapid and portable detection of ethylene in commercial fruit ripening storage rooms, we designed a smartphone-based optical fiber sensor (SOFS), which is composed of a 15 mW 365 nm laser for fluorescence signal excitation and a bifurcated fiber system for signal flow direction from probe to smartphone. Paired with a pyrene-tagged Grubbs catalyst (PYG) probe, our SOFS showed a wide linearity range up to 350 ppm with a detection limit of 0.6 ppm. The common gases in the warehouse had no significant interference with the results. The device is portable (18 cm × 8 cm × 6 cm) with an inbuilt power supply and replaceable optical fiber sensor tip. The images are processed with a dedicated smartphone application for RGB analysis and ethylene concentration. The device was applied in detection of ethylene generated from apples, avocados, and bananas. The linear correlation data showed agreement with data generated from a fluorometer. The SOFS provides a rapid, compact, cost-effective solution for determination of the fruit ethylene concentration dynamic during ripening for better fruit harvest timing and postharvest management to minimize wastage.

Surface enhanced FRET for sensitive and selective detection of doxycycline using organosilicon nanodots as donors.

In order to achieve on-site fluorescent detection of antibiotic doxycycline (DOC) residue, a new kind of fluorescent organosilicon nanodots (OSiNDs) was successfully constructed by a one-pot strategy and used as a novel ratiometric fluorescent probe. This method could enhance the fluorescence of DOC by conformational fixation on the surface of OSiNDs, and subsequently induced fluorescence resonance energy transfer (FRET). Control experimental results showed that phenylamine functional groups on the as-prepared OSiNDs possessed favorable interactions with DOC by hydrogen bond/π-π stacking, leading to both conformational change of DOC molecules and fluorescence resonance energy transfer process from OSiNDs to DOC. This method was then adapted and optimized for visual sensitive and selective detection of DOC based on ratiometric fluorescence signal, displaying a good linear range for DOC in the range of 1-35 µM with an excellent limit detection of ∼80 nM. Other tetracycline derivatives (TCs) and possible interferences have little influence on the determination of DOC using the method. The spike and recovery test of DOC in real water samples demonstrated the feasibility of the OSiNDs for DOC assay in practical samples and a test paper was fabricated with OSiNDs loading, achieving easy and visual detection of DOC by naked eyes.

Green-emitting carbon quantum dots as a dual-mode fluorescent and colorimetric sensor for hypochlorite.

In this work, green-emitting carbon quantum dots were successfully prepared through a facile one-step solid-state reaction method. The obtained green-emitting carbon dots (G-CDs) showed good fluorescence stability in NaCl aqueous solution and different pH values. Moreover, the G-CDs showed high sensitivity and selectivity for detecting hypochlorite by both fluorometry and colorimetry. Under the optimized condition, a highly sensitive detection of hypochlorite was established in the range of 0.2-100 µM and 10-150 µM for fluorescent and colorimetric methods, respectively. The corresponding limits of detection (LOD) were 0.0781 µM and 1.82 µM, respectively. Therefore, the G-CDs were successfully applied to determinate hypochlorite in actual water samples. In addition, a paper-based sensor loading with the G-CDs was also developed for rapid visual detection of hypochlorite. The results suggested that the G-CDs could be a promising candidate to detect hypochlorite.

On-site detection of As(III) based on silver nanoparticles aggregation mediated by phosphates using surface-enhanced Raman scattering (SERS).

A portable and simple method was developed for on-site selective determination of As(III) based on the SERS signal of As(III)-O vibration. The method relies on the synergistic effect of nanoparticles aggregation and analyte adsorption. Experimental results demonstrated that phosphate replaced the ligands of HH@Ag NPs, which in turn facilitated the adsorption of As(III) on the surface of HH@Ag NPs. The phosphate was introduced as an agglomerating agent to improve the detection ability of the method for As(III). The method shows good selectivity and linear relationship between 5 × 10-8 and 0.8 × 10-6 M, with the detection limit of 1.8 × 10-9 M. The method was applied to actual water samples and successfully detected As(III), indicating that the method could have application potential in actual detection scenarios.

Oxygen defects-induced charge transfer in Bi7O9I3 for enhancing oxygen activation and visible-light degradation of BPA.

Two-dimensional (2D) bismuth-based semiconductors have aroused intensive concern owing to their prominent photocatalytic activity for organic pollutants removal. In this work, a facile strategy for introducing oxygen vacancy in Bi-based oxyiodides (BixOyIz) sheet-like architectures to activate molecular oxygen was proposed. The structure, photoelectric properties and visible light (λ > 420 nm) induced photocatalytic activities of these samples for decomposition of bisphenol A (BPA) were systematically characterized and evaluated. The as-prepared Bi7O9I3 with a feeding Bi/I molar ratio of 1:1 exhibited the best photocatalytic activity comparable to those of similarly synthesized Bi7O9I3 with other molar ratios and BiOIO3 catalysts. The optimal Bi7O9I3 achieved excellent photocatalytic activity with 99.6 % degradation efficiency of BPA within 20 min and superior structural stability with 95.1 % degradation retention over 5 cycling tests. In addition, the resulting Bi7O9I3 sample displayed a high mineralization efficiency of BPA. Importantly, the plenty of oxygen vacancies (Vos) exsiting in Bi7O9I3 played the dominant role in both accelerating electron transfer and activating molecular oxygen to facilitate the generation of superoxide radical (O2·-) and singlet oxygen (1O2), thereby proceeding oxidative degradation of BPA molecules during photoreactions. The efforts and attempts are also extendable to synthesis other 2D photocatalysts, providing potential for effective charge-carrier separation and molecular oxygen activation.

Facile mitochondria localized fluorescent probe for viscosity detection in living cells.

Fluorescent probes act as a powerful tool to understand the function of intracellular viscosity, which are closely associated with many functional disorders and diseases. Herein we report a boron-dipyrromethene (4,4-difluoro-4-borata-3a,4a-diaza-s-indacene, BODIPY) group based new fluorescent probe (BV-1), which was synthesized facilely by a one-step Knoevenagel-type condensation reaction, to detect viscosity in living cells with high selectivity and sensitivity. DFT calculation demonstrated that the unsaturated moiety at the meso-position of BODIPY suppressed the fluorescence via twisted intramolecular charge transfer (TICT) mechanism in low viscosity media. By restricting the rotation of the molecular rotor, the fluorescence would be enhanced significantly with redshift in emission wavelength in high viscosity conditions. The fluorescence intensity ratio (log (I/I0)) at 570 nm showed a good linearity (R2 = 0.991) with the viscosity (log Î·) in the range of 2-868 cP. And the limit of detection (LOD) and limit of quantification (LOQ) for viscosity were calculated to be 0.16 cP and 0.54 cP, respectively. BV-1 was demonstrated to be mitochondria localized with low cytotoxicity. Utilizing the new probe BV-1, the changes in mitochondrial viscosity caused by monensin or nystatin have been monitored successfully in real time. This work will provide new efficient ways for the development of viscosity probes, which are expected to be used for the study of intracellular viscosity properties and functions.

Nitrogen doped carbon spheres with wrinkled cages for the selective oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furancarboxylic acid.

Nitrogen doped carbon spheres with wrinkled cages (NCSWCs), which were used for the first time as metal-free catalysts, exhibited high catalytic activity and selectivity in the oxidation of 5-hydroxymethylfurfural (HMF) to 5-formyl-2-furancarboxylic acid (FFCA) under base-free conditions using tert-butyl hydroperoxide (TBHP) as the oxidant. The mechanistic studies found that this reaction was catalyzed by the synergy between NCSWCs and TBHP. The density functional theory (DFT) calculations further suggested that the hydroperoxyl radicals from TBHP adsorbed on the carbon atoms adjacent to the graphitic N atoms are the active sites.

Noninvasive In Vivo Imaging and Monitoring of 3D-Printed Polycaprolactone Scaffolds Labeled with an NIR Region II Fluorescent Dye.

Significant progress has been made in fabricating porous scaffolds with ultrafine fibers for tissue regeneration. However, the lack of noninvasive tracking methods in vivo makes it impossible to track the fate of such scaffolds in situ. The development of near-infrared region II (NIR-II, 1000-1700 nm) dyes provides the possibility of performing noninvasive visualization with deep-tissue penetration and high spatial resolution in vivo. Herein, we developed a polycaprolactone (PCL) ink containing the small organic NIR-II dye SY-1030 and the fluorescently labeled macromolecular dye SY-COO-PCL and fabricated high-resolution NIR-II active scaffolds via electrohydrodynamic jet (EHDJ) printing. All printed scaffolds subcutaneously implanted in mice were clearly imaged one week after the operation. Compared with scaffolds containing SY-1030, the fluorescence intensity emitted from scaffolds containing SY-COO-PCL can be tracked for up to three weeks. Moreover, the image quality can be optimized by adjusting the dye concentration, laser power, and exposure time. The advantage of such NIR-II active scaffolds is evidenced by the lower dye concentration, longer tracking period, and better in vivo stability. We also demonstrated the biocompatibility and biodegradability of the scaffolds containing SY-COO-PCL over a 3-month period. The developed NIR-II active scaffolds have potential applications in biopolymer implant tracking, tissue reconstruction monitoring, and target-position-based drug delivery.

Role of nitroxyl (HNO) in cardiovascular system: From biochemistry to pharmacology.

Cardiovascular diseases are recognized to be a major cause of people morbidity and mortality. A host of stress signals contribute to the pathogenesis of cardiovascular disorders. Deficiency of hydrogen sulfide (H2S) or nitric oxide (NO) coordinately plays essential roles in the development of cardiovascular diseases. Recent studies have shown that interaction between the two gaseostransmitters, H2S and NO, may give rise to nitroxyl (HNO), one-electron-reduced product of NO. HNO is found to exhibit a variety of biological and pharmacological properties including positive inotropy and cardiovascular protective effects, etc. In this review, recent progresses regarding HNO generation, detection, biochemical and pharmacological functions are discussed.