Synthesis of Spiro Polycyclic N-Heterocycles and Indolecarbazoles via Merging Oxidative Coupling and Cascade Palladium-Catalyzed Intramolecular Oxidative Cyclization.

We report a step-economic strategy for the direct synthesis of spiro polycyclic N-heterocycles and indolecarbazole-fused naphthoquinones by merging oxidative coupling and cascade palladium-catalyzed intramolecular oxidative cyclization. In the protocol, bi-indolylnaphthoquinones were first synthesized by oxidative coupling of indoles and naphthoquinones. Subsequent cascade palladium-catalyzed intramolecular oxidative cyclization of bi-indolylnaphthoquinones gave spiro polycyclic N-heterocycles and indolecarbazoles. The intramolecular oxidative cyclization approach could also be realized by the presence or absence of iron catalysts under standard conditions. This protocol is featured with moderate to excellent yields, a wide substrate scope, and divergent structures of products.

Restraining the shuttle effect of polyiodides and modulating the deposition of zinc ions to enhance the cycle lifespan of aqueous Zn-I2 batteries.

The boom of aqueous Zn-based energy storage devices, such as zinc-iodine (Zn-I2) batteries, is quite suitable for safe and sustainable energy storage technologies. However, in rechargeable aqueous Zn-I2 batteries, the shuttle phenomenon of polyiodide ions usually leads to irreversible capacity loss resulting from both the iodine cathode and the zinc anode, and thus impinges on the cycle lifespan of the battery. Herein, a nontoxic, biocompatible, and economical polymer of polyvinyl alcohol (PVA) is exploited as an electrolyte additive. Based on comprehensive analysis and computational results, it is evident that the PVA additive, owing to its specific interaction with polyiodide ions and lower binding energy, can effectively suppress the migration of polyiodide ions towards the zinc anode surface, thereby mitigating adverse reactions between polyiodide ions and zinc. Simultaneously, the hydrogen bond network of water molecules is disrupted due to the abundant hydroxyl groups within the PVA additive, leading to a decrease in water activity and mitigating zinc corrosion. Further, because of the preferential adsorption of PVA on the zinc anode surface, the deposition environment for zinc ions is adjusted and its nucleation overpotential increases, which is favorable for the dense and uniform deposition of zinc ions, thus ensuring the improvement of the performance of the Zn-I2 battery. This investigation has inspired the development of a user-friendly and high-performance Zn-I2 battery.

Determination of moxifloxacin in milk using a ratiometric fluorescent sensor based on Ag-MOF@curcumin.

Moxifloxacin (MFX) has attracted increasing public concern recently, and the development of a simple and effective analysis method has become a research focus. In this work, a simple, sensitive and ratiometric fluorescent sensor based on Ag-MOF@curcumin was designed and investigated. Ag-MOF@curcumin displays emission at 410 nm and 475 nm under excitation at 330 nm. When MFX is added, a new emission peak appears at 500 nm, and the F500/F410 ratio has a linear relationship with the MFX concentration in the range 0-35 µmol L-1 with a low LOD (0.179 µmol L-1). Finally, the developed sensor was used for the determination of MFX in milk. This work provides an excellent fluorescent sensor for highly selective and rapid detection of MFX residues.

Ammonia-assisted Ni particle preferential deposition in Ni-Fe pyrophosphates on iron foam to improve the catalytic performance for overall water splitting.

Designing efficient and cost-effective electrocatalysts for overall water splitting remains a major challenge in hydrogen production. Herein, ammonia was introduced to pyrophosphate chelating solution assisted Ni particles preferential plating on porous Fe substrate to form coral-like Ni/NiFe-Pyro electrode. The pyrophosphate with multiple complex sites can couple with nickel and iron ions to form an integrated network structure, which also consists of metallic nickel due to the introduction of ammonia. The large network structure in Ni/NiFe-Pyro significantly enhances the synergistic effect between nickel and iron and then improves the electrocatalytic performance. As a result, the coral-like Ni/NiFe-Pyro@IF exhibits good electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The electrolyzer assembled with Ni/NiFe-Pyro@IF as cathode and anode just needs a low water-splitting voltage of 1.54 V to obtain the current density of 10 mA cm-2. Meanwhile, the stability test of Ni/NiFe-Pyro@IF is performed at the current densities ranging from 10 to 400 mA cm-2 for 50 h without any significant decay, indicating robust catalytic stability for overall water splitting. This strategy for synthesizing metal/metal pyrophosphate composites may provide a new avenue for future studies of efficient bifunctional electrocatalysts.

Synthesis of the [6-6-7-5-5] Pentacyclic Core of Calyciphylline N.

A new approach for the concise 11-step synthesis of the [6-6-7-5-5] BCDEF pentacyclic core of calyciphylline N is described. A type II [5 + 2] cycloaddition was employed to construct the strained BCD skeleton, which encompasses the challenging bicyclo[2.2.2] and bicyclo[4.3.1] ring systems. With a regio- and diastereoselective Lu's [3 + 2] cycloaddition, followed by intramolecular aldol cyclization and elimination, the desired [5-5]-fused EF ring system has been successfully installed, resulting in the complete carbocyclic skeleton of calyciphylline N.

Boron difluoride modified zinc metal-organic framework-based "off-on" fluorescence sensor for tetracycline and Al3+ detection.

A novel fluorescence "off-on" probe was developed using a boron difluoride-modified zinc metal-organic framework (Zn-MOF3) for sensitive determination of tetracycline (TC) and Al3+. The Zn-MOF3 has excellent optical property and good applicability in aqueous phase. The fluorescence recorded at 436 nm was quenched at the excitation wavelength of 336 nm. Signal-off detection of tetracycline via fluorescence quenching of Zn-MOF3 is based on the inner filter effect. Fluorescence on-off-on detection of Al3+ occurs via the specific binding between tetracycline and Al3+. The limits of detection for TC and Al3+ were 28.4 nM and 106.7 nM, respectively. This probe exhibited high selectivity which was used for the determination of TC and Al3+ with satisfied recoveries (89.8 to 105.6% for TC, 90.0 to 110.4% for Al3+) and good precision (< 5%) in milk. The developed sensor represents the first "off-on" system for fluorescence detection of TC and Al3+ based on Zn-MOF3 with a better aspect of the innovation.

CB[8]- and triarylboron-based supramolecular organic framework for microRNA detection, tumor-targeted drug delivery, and photodynamic therapy.

Supramolecular organic frameworks (SOFs) are widely used for biological detection and drug delivery. In this study, a SOF system was fabricated through the self-assembly of photosensitive triarylboron (TAB), TAB-6-methyl, and CB[8]. The maximum fluorescence emission of TAB-6-methyl was greatly enhanced and red-shifted from 560 nm to 610 nm after SOF formation. The SOF can specifically respond to a microRNA by dissembling and then combining with microRNA, which is accompanied by a fluorescence shift from 610 nm to 560 nm, thus providing a ratiometric readout for microRNA detection. The photosensitivity of TAB-6-methyl can be further improved by forming a SOF, which can be used in photodynamic therapy. By constructing another guest molecule, TAB-5-1-cRGD, we successfully embedded cRGD in the SOF system to improve its tumor-targeting ability. Moreover, we used this SOF system as a fluorescence imaging probe for targeted tumor imaging and as a drug carrier system for loading DOX to achieve combined photodynamic and chemotherapy treatment of tumors.

Polyaniline-modified halloysite nanotubes as high-efficiency adsorbents for removing of naproxen in the presence of different heavy metals.

In this work, novel adsorbent polyaniline-modified halloysite nanotubes (HNT@PA-2) were synthesized successfully by in situ polymerization to increase active adsorption sites. With the increase of the amount of aniline, the adsorption capacity of naproxen becomes higher. The optimal ratio of halloysite nanotubes to aniline was 1 : 2. The effects of adsorption conditions such as pH, mass of HNT@PA-2, time and initial concentration of naproxen were systematically researched. The optimum adsorption for naproxen was pH 9, mass 10 mg and contact time 4 h. The adsorption of naproxen conformed to the pseudo-first-order kinetic model, and the maximum adsorption capacity was 242.58 mg g-1 at 318 K. In addition, the effects of ionic strength and different heavy metals also were studied. Higher ionic strength of the system could influence the adsorption of naproxen. The effects of Al3+, Pb2+, Zn2+ and Co2+ ions on the adsorption of naproxen could be ignored, while Cu2+ and Fe3+ ions inhibited the process. The mechanisms for naproxen adsorbed by the HNT@PA-2 were π-π interaction, hydrogen bonding and hydrophobic reaction. Therefore, the HNT@PA-2 could be used for the treatment of medical wastewater for removing naproxen.

Effect of Preheating Whey Protein Concentrate on the Stability of Purple Sweet Potato Anthocyanins.

Anthocyanins (ANs) have strong antioxidant activities and can inhibit chronic diseases, but the instability of ANs limits their applications. The conservation of preheating whey protein concentrate (WPC) on the stability of purple sweet potato ANs was investigated. The retention of ANs in WPC-ANs was 85.88% after storage at 25 °C for 5 h. WPC-ANs had higher retention of ANs in heating treatment. The retention rates of ANs in WPC-ANs exposed to light and UV lamps for 6 h were 78.72% and 85.76%, respectively. When the concentration of H2O2 was 0.50%, the retention rate of ANs in the complexes was 62.04%. WPC-ANs' stability and antioxidant activity were improved in simulated digestive juice. The WPC-ANs connection was static quenching, and the binding force between them was a hydrophobic interaction at one binding site, according to the fluorescence quenching spectroscopy. UV-visible absorption spectroscopy and Fourier transform infrared spectroscopy (FTIR) analysis further indicated that the secondary structure and microenvironment of amino acid residues in WPC can be impacted by the preheating temperature and preheating times of WPC. In conclusion, preheating WPC can successfully preserve the stability of purple sweet potato ANs by binding to them through a non-covalent interaction.

Aggregation-induced type I&II photosensitivity and photodegradability-based molecular backbones for synergistic antibacterial and cancer phototherapy via photodynamic and photothermal therapies.

The clinical applications of phototherapy nanomaterials are still limited due to concerns regarding their phototoxicity and efficacy. Herein, we report a novel type of D-π-A molecular backbone that induces type I/II photosensitivity and photodegradability by forming J-aggregates. The photodegradation rate can be regulated by changing the donor groups to regulate the photosensitivity of their aggregates because the photodegradability performance results from their oxidation by 1O2 generated by their type II photosensitivity. AID4 NPs possess faster photodegradation because of their better type I&II photosensitivity, which can also self-regulate by inhibiting type II and improving type I under hypoxic conditions. Moreover, they exhibited good photothermal and photoacoustic performance for improving their therapeutic effect by a synergistic effect and achieving photoacoustic imaging in vivo. The experimental result also showed that they can be effective for antibacterial and anti-tumor treatment and the photodegradation products of AID4 NPs possess low biological toxicity in the dark or under light. This study could provide a novel strategy for improving the safety and treatment effects of phototherapy.

Synthesis and characterization of a julolidine-based electro-optic molecular glass.

AIM: Organic electro-optic (EO) materials have recently gained considerable attention owing to their advantages compared to inorganic EO materials. Among different kinds of organic EO materials, organic EO molecular glass exhibits desired prospect because of its high chromophore loading density and large macroscopic EO activity. INTRODUCTION: The objective of this study is to design and synthesize a novel organic EO molecular glass JMG utilizing julolidine moiety as the electron donor, thiophene moiety as the conjugated bridge, trifluoromethyl substituted tricyanofuran derivate (Ph-CF3-TCF) as the electron acceptor. METHOD: The JMG's structure was characterized through NMR and HRMS. The photophysical property, glass transition temperature, first hyperpolarizability (ß) and dipole moment (µ) of JMG were determined through UV-vis spectra, DSC test and DFT calculation. RESULTS: JMG's Tg reached to 79 °C and it can form high-quality optical film. The theoretical calculation shows that the first hyperpolarizability (ß) and dipole moment (µ) of JMG were calculated to 730×10-30 esu and 21.898 D. After connecting poling with the poling voltage of 49 V/µm at 90 ℃for 10 min, the highest EO coefficient (r33) of the poled JMG films reached to 147 pm/V. CONCLUSION: A novel julolidine-based NLO chromophore with two tert-butyldiphenylsilyl (TBDPS) groups was successfully prepared and characterized. TBDPS group is introduced as the film-forming group, and it also plays the role of isolation group, which can suppress the electrostatic interaction between chromophores, improve the poling efficiency and further enhance the EO activity. The excellent performances endow JMG with potential applications in device fabrication.

Ferryl Ion in the Photo-Fenton Process at Acidic pH: Occurrence, Fate, and Implications.

Fenton processes produce reactive species that can oxidize organic compounds in natural and engineered systems. While it is well-documented that Fenton reactions produce hydroxyl radical (HO•) under acidic conditions, we demonstrated the generation of ferryl ion (FeIVO2+) in the UV/Fe(III) and UV/Fe(III)/H2O2 systems at pH 2.8 using methyl phenyl sulfoxide (PMSO) as the probe compound. Moreover, we clarified that FeIVO2+ is parallelly formed via the oxidation of Fe(III) by HO• and the O-O homolysis of [FeIII-OOH]2+ in the photo-Fenton process. The rate constant for the reaction between HO• and Fe3+ measured by laser flash photolysis was 4.41 × 107 M-1 s-1. The rate constant and quantum yield for thermal and photo O-O homolysis of [FeIII-OOH]2+ complex were 1.4 × 10-2 s-1 and 0.3, respectively, which were determined by fitting PMSO2 formation. While FeIVO2+ forms predominantly through the reaction between HO• and Fe3+ in the absence of H2O2, the relative contribution of [FeIII-OOH]2+ O-O homolysis to FeIVO2+ formation highly depends on the molar ratio of [H2O2]0/[Fe(III)]0, the level of HO• scavenging, and incident irradiance in the UV/Fe(III)/H2O2 system. Accordingly, an optimized kinetic model was developed by incorporating FeIVO2+-involved reactions into the conventional photo-Fenton model, which can accurately predict Fe(II) formation and contaminant decay in the UV/Fe(III) and UV/Fe(III)/H2O2 systems. Our study illuminated the underlying formation mechanism of reactive oxidative species in the photo-Fenton process and highlighted the role of FeIVO2+ evolution in modulating the iron cycle and pollutant abatement therein.

Engineering of metal-organic framework nanomaterials on long-period fiber grating for acetone vapor sensing.

Metal-organic framework (MOF) material is one of the most promising porous nanomaterials for volatile organic compound (VOC) adsorption and sensing. The large surface area and the high porosity of MOF contribute to the high sensitivity of MOF-based VOC sensors. In this study, we engineer the coating of the zeolitic imidazolate framework material ZIF-8 grown on the surface of a long-period fiber grating (LPFG) for acetone vapor sensing. Being a periodic structure formed in a single-mode optical fiber, an LPFG is designed to couple light from the core to the cladding of the fiber at a specific resonance wavelength. Adsorption of acetone vapor molecules in the framework of the ZIF-8 coating can change the refractive index of the coating and cause a shift in the resonance wavelength of the LPFG. The sensitivity of the resonance shift of the LPFG to the acetone vapor concentration depends strongly on the thickness of the ZIF-8 coating. To create a dense ZIF-8 coating, at least five growth cycles of ZIF-8 (30 min growth for one cycle) are required, and nine growth cycles can create a 500 nm thick coating. The LPFG coated with nine growth cycles of ZIF-8 provides a high sensitivity of 21.9 nm ppm-1, a low detection limit of 1.4 ppm, and a wide detection range of about 1500 ppm. Our results can facilitate the development of high-performance optical fiber sensors based on MOF for VOC detection.

Novel fluorescence sensor for the selective recognition of tetracycline based on molecularly imprinted polymer-capped N-doped carbon dots.

A novel fluorescent probe based on molecularly imprinted polymers (MIPs) coupled with N-doped carbon dots (CDs) was prepared and used for specific recognition and sensitive determination of tetracycline (TC). N-doped CDs were synthesized using citric acid as a carbon source and ethylenediamine as a nitrogen source by a microwave assisted pyrolysis method. The determination conditions such as the solvents, material amount, pH value, and temperature were optimized. The CDs-MIPs have the best quenching on TC in water. The proposed method used for TC determination in milk powder samples had a detection limit of 0.054 µg mL-1 and a wide range of 0.5-30 µg mL-1. Meanwhile, satisfactory recoveries were obtained ranging from 95 to 108%. Oxytetracycline, chlorotetracycline and most of the coexisting substances showed no obvious interference indicating that the CDs-MIP probe exhibited high selectivity due to the presence of imprinted sites. Charge transfer from CDs-MIPs to TC may be through the mechanism of fluorescence quenching. This work gives a feasible strategy for the synthesis of N-doped carbon dot based molecularly imprinted polymers used as a fluorescent sensor in the food analysis field.

A Multifactor Quantitative Assessment Model for Safe Mining after Roof Drainage in the Liangshuijing Coal Mine.

To prevent coal mine roof water damage, the water generally needs to be evacuated in advance. It can be mined with the water inrush risk assessed as safe. However, a single index is often employed in the water safety evaluation after the roof drainage, which causes a large gap between the evaluation results and the actual situation. Therefore, the evaluation cannot be effectively used to guide the safety mining in the working face. In this paper, based on the hydrogeological data of the Liangshuijing coal mine, a multifactor water inrush risk assessment model (IAHP-EWM) and multifactor index system are established for assessing the water inrush risk before and after the roof drainage. The improved AHP method and the entropy weight method are adopted in the model to determine the index weight. This combined way avoids the excessive subjectivity and objectivity of the index weight. A″ Fold undulation degree (Fud )″ is innovatively proposed to quantify the impact of the spatial relief of folds on water inrush in the multifactor index system. The IAHP-EWM model is applied to evaluate the risk of roof water inrush in the 42205 working face of the Liangshuijing coal mine. The evaluation results show that the water inrush risk is ″high″ when the water is not dredged, and the water inrush risk is ″low″ after the water is dredged, which are consistent with the actual water inflow data and evaluation results, which verifies the accuracy of the model. The application results of the IAHP-EWM model in the 42202, 42203, and 42204 working faces verify its universal applicability in the Liangshuijing mining area. It can provide a reference for the evaluation of the roof water damage control effect during coal seam mining.

[Regulation of plant iron homeostasis by abscisic acid: a review].

Iron (Fe) is an important trace element involved in many important plant physiological and metabolic processes such as photosynthesis, respiration and nitrogen metabolism. Plants maintain iron homeostasis through absorption, transporting, storage and redistribution of iron. Iron metabolism is strictly regulated in plants. Iron regulatory transcription factors and iron transporters constitute the regulatory network of plant iron absorption and transport in plants. Ferritin and iron transporter jointly regulate the response to excess iron in plants. In recent years, important progress has been made in understanding how abscisic acid (ABA) regulates iron metabolism in plants. ABA may be used as a signal to regulate the absorption, transportation and reuse of Fe, or to relieve the symptoms of iron stress by regulating the oxidative stress responses in plants. In order to gain deeper insights into the crosstalk of ABA and iron metabolism in plants, this review summarized the mechanisms of iron absorption and transport and metabolic regulatory network in plants, as well as the mechanisms of ABA in regulating iron metabolism. The relationship between ABA and FER-like iron deficiency-induced transcription factor (FIT), iron-regulated transporter 1 (IRT1), and oxidative stress of iron deficiency were highlighted, and future research directions were prospected.

Extracting Total Anthocyanin from Purple Sweet Potato Using an Effective Ultrasound-Assisted Compound Enzymatic Extraction Technology.

This study aimed to develop an effective technique for extracting total anthocyanins from purple sweet potato (Mianzishu 9) (PSP9) by ultrasound-assisted compound enzymatic extraction (UAEE). Single-factor experiments, Plackett-Burman experimental design, and response surface methodology were utilized for optimizing extraction conditions, and the antioxidant activities were evaluated. Anthocyanins were also measured using an ultra-performance liquid chromatograph linked to a mass spectrometer (UPLC-MS). The maximum yield of total anthocyanins was 2.27 mg/g under the following conditions: the ethanol concentration was 78%, the material-to-liquid ratio was 1:15 g/mL, the enzyme ratio (cellulase: pectinase: papain) was 2:2:1 and its hydrolysis was at 41 °C, pH = 4.5, 1.5 h, the ultrasonication was at 48 °C and conducted twice for 20 min each time. In addition to higher yield, anthocyanins extracted from purple sweet potato by UAEE showed great ability to scavenge DPPH (IC50 of 0.089 µg/mL) and hydroxyl radicals (IC50 of 100.229 µg/mL). Five anthocyanins were found in the purple sweet potato extract from UAEE. Taken together, the ultrasound-assisted compound enzymatic method can rapidly and effectively extract anthocyanins with greater antioxidant capacity from purple sweet potato.

Fluorescence determination of chloramphenicol in milk powder using carbon dot decorated silver metal-organic frameworks.

Carbon dot decorated silver metal-organic frameworks (CD-MOFs) were successfully synthesized at room temperature by adding CDs during the formation of Ag-MOFs. The CD-MOFs have excellent optical property, stability, and good fluorescence intensity in water compared with other solvents. The fluorescence intensity of CD-MOFs was relatively stable in the range of pH 5-9. It was used to construct a sensitive and reliable fluorescent sensor for the determination of chloramphenicol (CAP). When the CAP was introduced into the CD-MOFs, the fluorescence at 427 nm was quenched at the excitation wavelength of 332 nm. Wide linear relationships were established for CAP with a limit of detection of 44 nM. The fluorescent sensor has been applied to determine CAP in milk powder sample with satisfied recoveries (104 to 109%) and good precision (< 4%). The photoinduced electron-transfer is the most important mechanism contributing to the fluorescence quenching. The synthesized CD-MOFs provide a new orientation for fluorescence determination of chloramphenicol in real samples.

Construction of MnxCoyO4/Ti electrocatalysts for efficient bifunctional water splitting.

In this work, we report the design and synthesis of non-noble metal-based electrocatalysts for effective overall water splitting in alkaline solutions for the development of hydrogen energy. The electrocatalysts were synthesized by a one-step hydrothermal method similar to microflower structure electrocatalysts. The synergistic effect between the special Echinops sphaerocephalus nanostructure and the nanowire can greatly improve the conductivity of the nanomaterial due to its high activity quality, fast ion transport, and exposure of more active sites, thus resulting in a better catalytic activity and a longer material stability of the electrocatalyst. For MnxCoyO4/Ti in alkaline aqueous solutions, a current density of 10 mA cm-2 is required when the voltage is only 1.60 V. In addition, the hydrogen evolution activity of electrocatalysts is 168 mV at 10 mA cm-2, the Tafel slope is 174 mV dec-1, and the oxygen evolution activity of electrocatalysts is 229 mV at 10 mA cm-2, which showed good long-term stability within 12 h, even better than that of previously reported electrocatalysts.

Molecular-engineered highly photosensitive triarylphosphine oxide compounds for apoptosis imaging and selectively inducing apoptosis of tumor cells by photodynamic therapy.

Although photodynamic therapy (PDT) has wide applications, tumor-targeting probes with high photosensitivity or apoptosis-monitoring capability, which possess low phototoxicity and can be used for evaluating therapeutic efficacy, are still scarce. In this study, we constructed a series of highly photosensitive probes by introducing multivalent positive charges around propeller-like triarylphosphine oxide compounds. Some of them can be used to detect apoptosis by selectively entering apoptotic cells in the presence of living or necrotic cells. Among them, OTPP-6-Amyl can target SKOV-3 cells by binding to their membrane in a short time and move to mitochondria with prolonging time and can be further applied for imaging SKOV-3 tumors in vivo, whereas for various apoptotic cells, it mainly enters the nucleus. Its high photosensitivity can be used to induce apoptosis in SKOV-3 cells without affecting the survival of other cells. By functionalizing with cRGD, another probe was constructed to target U87MG cells and induce their apoptosis by PDT, and it can also pass through the blood-brain barrier.