Organocatalytic allylic alkylation of alkyne-substituted MBH carbonates: access to quaternary carbon-containing 1,4-enynes.

A DABCO-catalyzed allylic alkylation of tertiary propargylic alcohol-derived MBH carbonates with nitromethane was developed. A series of substituted 1,4-enynes with an all-carbon quaternary stereocenter were efficiently obtained in moderate to high yields. The synthetic utility of the product was demonstrated by facile synthesis of 1,4-enyne-embedded 2-pyrrolidinones.

Cross-linked polyaniline for production of long lifespan aqueous iron||organic batteries with electrochromic properties.

Aqueous iron batteries are appealing candidates for large-scale energy storage due to their safety and low-cost aspects. However, the development of aqueous Fe batteries is hindered by their inadequate long-term cycling stability. Here, we propose the synthesis and application as positive electrode active material of cross-linked polyaniline (C-PANI). We use melamine as the crosslinker to improve the electronical conductivity and electrochemical stability of the C-PANI. Indeed, when the C-PANI is tested in combination with a Fe metal negative electrode and 1 M iron trifluoromethanesulfonate (Fe(TOF)2) electrolyte solution, the coin cell can deliver a specific capacity of about 110 mAh g-1 and an average discharge voltage of 0.55 V after 39,000 cycles at 25 A g-1 with a test temperature of 28 °C ± 1 °C. Furthermore, mechanistic studies suggest that Fe2+ ions are bonded to TOF- anions to form positively charged complexes Fe(TOF)+, which are stored with protons in the C-PANI electrode structures. Finally, we also demonstrate the use of C-PANI in combination with a polymeric hydrogel electrolyte to produce a flexible reflective electrochromic lab-scale iron battery prototype.

Electro-oxidation induced O-S cross-coupling of quinoxalinones with sodium sulfinates for synthesizing 2-sulfonyloxylated quinoxalines.

The functionalization of quinoxalinones is synthetically and biologically appealing, however, C2 functionalized quinoxalinones is not reported via environmentally friendly approach. Herein, we disclosed C2-O sulfonylation of quinoxalinones via our developed electrochemical oxidative O-S coupling strategy for synthesizing 2-sulfonyloxylated quinoxalines. Applying this protocol, quinoxalin-ones and sodium sulfinates as the starting materials, a wide range of 2-sulfonyloxyl quinoxaline derivatives were obtained in moderate to good yields with good functional-group tolerance under mild conditions without additional oxidants. The utility of this methodology and the sulfonyloxyl handles was demonstrated trough gram-scale preparation and the synthesis of 2-substituted quinoxaline-based bioactive molecules, respectively.

Synergistic mechanism of Ni(OH)2/NiMoS heterostructure electrocatalyst with crystalline/amorphous interfaces for efficient hydrogen evolution over all pH ranges.

Designing and fabricating efficient electrocatalysts is a practical step toward the commercial application of the efficient hydrogen evolution reaction (HER) over all pH ranges. Herein, novel Ti@Ni(OH)2-NiMoS heterostructure with interface between crystalline Ni(OH)2 and amorphous NiMoS was rationally designed and fabricated on Ti mesh (denoted as Ti@Ni(OH)2-NiMoS). Acid etching and calcination experiments helped in accurate elucidation of the synergistic mechanism as well as the vital role on crystalline Ni(OH)2 and amorphous NiMoS. In acidic solutions, the HER performance of Ti@Ni(OH)2-NiMoS was mainly attributed to the amorphous NiMoS. In neutral, alkaline, and natural seawater solutions, the HER performance was mainly determined by the synergistic interface behaviors between the Ni(OH)2 and NiMoS. The crystalline Ni(OH)2 accelerated water dissociation kinetics, while the amorphous NiMoS provided abundant active sites and allowed for fast electron transfer rates. To deliver current densities of 10 mA·cm-2 in acidic, neutral, alkaline, and natural seawater solutions, the Ti@Ni(OH)2-NiMoS required overpotentials of 138, 198, 180 and 371 mV, respectively. This paper provides general guidelines for designing efficient electrocatalyst with crystalline/amorphous interfaces for efficient hydrogen evolution over all-pH ranges.

Ethylenediamine-assisted hydrothermal synthesis of NiCo2O4 absorber with controlled morphology and excellent absorbing performance.

In recent years, developing excellent electromagnetic wave (EMW) absorbers with small thickness and large bandwidth is an effective strategy to deal with the seriously EMW interferes in military and civil field. The morphology of absorbers has profound effects on their EMW absorption performance. Herein, ethylenediamine (EDA) was applied to EMW absorbing field as morphology control agent for the first time (as far as we know) for the synthesis of nickel cobaltate (NiCo2O4) absorber, and the effect of EDA content on the morphology and EMW absorbing performance was also investigated elaborately. As a bidentate ligand and structure-directing reagent, EDA controlled the morphology of NiCo2O4 by reducing the rate of nucleation and crystal growth through the complexation with metal ions, and adjusting the growth rate of different facets through the selective binding of amino to certain surfaces. The study found that the morphology of NiCo2O4 changed from three-dimensional urchin-like structures to two-dimensional nanosheets with the increase of EDA content, and meanwhile the dielectric loss property decreased, which led to decline in EMW attenuation properties. The urchin-like NiCo2O4 absorber at a molar ratio of 0.5 (EDA: metal ions) exhibited optimum absorption properties with a small thickness of 1.70 mm and large effective absorption bandwidth (EAB) of 5.81 GHz (12.19-18 GHz). The excellent EMW absorbing properties mainly originate from remarkable dipole polarization induced by oxygen vacancies and lattice defects, interface polarization stemming from the interfaces of NiCo2O4 fibers, and multiple reflections and scattering in its unique urchin-like structures. This work provides a simple method for absorber with controlled morphologies, and also expands the family members of Co-based ferrite with outstanding absorbing performance.

Biomimetic Hydroxyapatite on Graphene Supports for Biomedical Applications: A Review.

Hydroxyapatite (HA) has been widely used in fields of materials science, tissue engineering, biomedicine, energy and environmental science, and analytical science due to its simple preparation, low-cost, and high biocompatibility. To overcome the weak mechanical properties of pure HA, various reinforcing materials were incorporated with HA to form high-performance composite materials. Due to the unique structural, biological, electrical, mechanical, thermal, and optical properties, graphene has exhibited great potentials for supporting the biomimetic synthesis of HA. In this review, we present recent advance in the biomimetic synthesis of HA on graphene supports for biomedical applications. More focuses on the biomimetic synthesis methods of HA and HA on graphene supports, as well as the biomedical applications of biomimetic graphene-HA nanohybrids in drug delivery, cell growth, bone regeneration, biosensors, and antibacterial test are performed. We believe that this review is state-of-the-art, and it will be valuable for readers to understand the biomimetic synthesis mechanisms of HA and other bioactive minerals, at the same time it can inspire the design and synthesis of graphene-based novel nanomaterials for advanced applications.

Improving the size uniformity of dendritic fibrous nano-silica by a facile one-pot rotating hydrothermal approach.

Dendritic fibrous nano-silica (DFNS), also well-known as KCC-1, possesses three-dimensional center-radial nanochannels and hierarchical nanopores. Compared with conventional mesoporous materials like SBA-15, these special structural characteristics endow DFNS with more accessible internal space, higher specific surface area, larger pore volume, etc. Even though great progress has been achieved, the as-prepared KCC-1 nanospheres exhibit extremely non-uniform diameters and their sizes differ enormously in almost all available traditional synthesis approaches. Herein, a facile and low-cost one-pot rotating hydrothermal approach is adopted to improve the size uniformity of dendritic fibrous nano-silica. Stirring rates of 30, 60, 90, 120, and 150 (the maximum) revolutions per minute (rpm) can influence KCC-1 uniformity to certain extents. Among them, 60 rpm can be considered to be an ideal stirring rate for relatively uniform KCC-1 because of the best sufficient contact of reaction phases. A plausible synthesis mechanism can be explained in terms of continuously variable stress conditions of the reaction mother liquor (i.e., the bicontinuous microemulsion) during the fabrication process. To be specific, except for gravity (G), this technique brings about the centrifugal force (F) stemming from the stirring rate, and the buoyancy (f) originated from vigorous reversal of organic phase in the reaction solution. These forces synergistically mix organic phase and water phase, which generates new bicontinuous microemulsion droplets (BMDs) to supplement the consumed ones. All in all, this approach as well as the synthesis equipment is simple, inexpensive, and reproducible for large-scale KCC-1 preparation with improved size uniformity.

Dendritic fibrous nano-silica & titania (DFNST) spheres as novel cataluminescence sensing materials for the detection of diethyl ether.

Selective and controllable cataluminescence (CTL) sensors for volatile organic compounds (VOCs) are significant for chemical safety, environmental monitoring, health effects on human beings, and so forth. Most of the exploited CTL-based sensors suffer relatively low response and poor selectivity because of their high sensitivities to interferential substances. In this investigation, dendritic fibrous nano-silica & titania (DFNST) spheres have been synthesized as novel sensing materials and the corresponding DFNST-based CTL sensor has been fabricated to detect diethyl ether with high selectivity via a method of utilizing one 440 nm bandpass filter. The as-prepared DFNST hybrids not only keep the excellent dendritic fibrous morphology but also bear ca. 21 wt% catalytic titanium oxide of anatase crystalline structure. The DFNST-based sensor exhibits extremely strong CTL emission at 440 nm toward diethyl ether against other VOCs like acetone, ethyl acetate, butanol, and so forth. The high response can be attributed to the unique architectural texture of DFNST. Under the optimum parameters, ether could be easily detected in a wide range from 2.0 to 40.0 mM with a fine detection limit of 1.55 mM (S/N = 3). Furthermore, the working life of this CTL sensor is satisfactory with outstanding stability and durability, far from damaging the morphology and activity of the DFNST sensing material. In conclusion, it is expected that this novel sensing material, the relevant CTL sensor, and the approach of employing the bandpass filter will be significant for the detection of diethyl ether in actual applications.

Crystallization-Induced Emission Enhancement of a Deep-Blue Luminescence Material with Tunable Mechano- and Thermochromism.

Organic luminescent materials with the ability to reversibly switch the luminescence when subjected to external stimuli have attracted considerable interest in recent years. However, the examples of luminescent materials that exhibit multiresponsive properties are rarely reported. In this work, a new stimuli-responsive dye P1 is designed and synthesized with two identical chromophores of naphthalimide, one at each side of an amidoamine-based spacer. This amide-rich molecule offers many possibilities for forming intra- and intermolecular hydrogen bond interactions. Particularly, P1 has an intrinsic property of cocrystallizing with methanol. Compared with the pristine P1 sample, the as-prepared two-component cocrystalline material displays an exceptive deep-blue emission, which is extremely rare among naphthalimide-based molecules in the solid state. Furthermore, the target material exhibits an obvious mechanochromic fluorescent behavior and a large spectral shift under force stimuli. On the other hand, the cocrystalline material shows an unusual "turn off" thermochromic luminescence accompanied by solvent evaporation. Moreover, using external stimuli to reversibly manipulate fluorescent quantum yields is rarely reported to date. The results demonstrate the feasibility of a new design strategy for solid-state luminescence switching materials: the incorporation of solvents into organic compounds by cocrystallization to obtain a crystalline state luminescence system.

A 1,2-propylene oxide sensor utilizing cataluminescence on CeO2 nanoparticles.

A simple and sensitive gas sensor was proposed for the determination of 1,2-propylene oxide (PO) based on its cataluminescence (CTL) by oxidation in the air on the surface of CeO2 nanoparticles. The luminescence characteristics and optimal conditions were investigated in detail. Under optimized conditions, the linear range of the CTL intensity versus the concentration of PO was 10-150 ppm, with a correlation coefficient (r) of 0.9974 and a limit of detection (S/N = 3) of 0.9 ppm. The relative standard deviation for 40 ppm PO was 1.2% (n = 7). There was no or only weak response to common foreign substances including acetone, formaldehyde, ethyl acetate, acetic acid, chloroform, propanol, carbon tetrachloride, ether and methanol. There was no significant change in the catalytic activity of the sensor for 100 h. The proposed method was simple and sensitive, with a potential of detecting PO in the environment and industry.

Low temperature CO sensor based on cataluminescence from plasma-assisted catalytic oxidation on Ag doped alkaline-earth nanomaterials.

Based on cataluminescence from plasma-assisted catalytic oxidation, a low temperature CO sensor was fabricated. With Ag doped alkaline-earth catalyst as sensing element, air as discharge gas, carrier gas and oxidant supplier, significant cataluminescence was achieved at low temperature, demonstrating a potential low-consumption and portable sensor of CO.

A chemiluminescence sensor array for discriminating natural sugars and artificial sweeteners.

In this paper, we report a chemiluminescence (CL) sensor array based on catalytic nanomaterials for the discrimination of ten sweeteners, including five natural sugars and five artificial sweeteners. The CL response patterns ("fingerprints") can be obtained for a given compound on the nanomaterial array and then identified through linear discriminant analysis (LDA). Moreover, each pure sweetener was quantified based on the emission intensities of selected sensor elements. The linear ranges for these sweeteners lie within 0.05-100 mM, but vary with the type of sweetener. The applicability of this array to real-life samples was demonstrated by applying it to various beverages, and the results showed that the sensor array possesses excellent discrimination power and reversibility.

Development of an analytical method for the determination of beta2-agonist residues in animal tissues by high-performance liquid chromatography with on-line electrogenerated [Cu(HIO6)2]5- -luminol chemiluminescence detection.

A novel method was developed for the simultaneous determination of beta2-agonist residues such as terbutaline, salbutamol, and clenbuterol by high-performance liquid chromatography (HPLC) coupled with chemiluminescence (CL) detection. The procedure was based on the enhancement effect of beta2-agonists on the CL reaction between luminol and the complex of trivalent copper and periodate ([Cu(HIO6)2]5-), which was on-line electrogenerated by constant current electrolysis. The HPLC separation used a Nucleosil RP-C18 column (250 mm x 4.6 mm i.d., 5 microm; pore size, 100 A) with a mobile phase consisting of 90% acetonitrile and 10% aqueous ammonium acetate (20 mmol L-1, pH 4.0) at a flow rate of 1.0 mL min-1. The effects of several parameters on the HPLC resolution and CL emission were studied systematically. Liver samples were hydrolyzed with beta-glucuronidase followed by a solid-phase extraction procedure using Waters OasisMCX cartridges. Under optimum conditions, the limits of detection at a signal-to-noise ratio of 3 ranged from 0.007 to 0.01 ng g-1 and the limits of quantification at a signal-to-noise ratio of 10 ranged from 0.023 to 0.033 ng g-1 for three beta2-agonists. The relative standard deviations (RSDs) of intra- and interday precision were below 4.5%. The average recoveries for beta2-agonists (spiked at the levels of 0.05-5.0 ng g-1) in pig liver ranged from 84 to 110%, and the RSDs of the quantitative results were from 1.6 to 7.2%. The proposed method was successfully applied to the determination of beta2-agonist residues in pig liver samples.

Determination of propylthiouracil and methylthiouracil in human serum using high-performance liquid chromatography with chemiluminescence detection.

Based on the sensitizing effect of formaldehyde on the chemiluminescence (CL) reaction of propylthiouracil (PTU) and methylthiouracil (MTU) with acidic potassium permanganate and the combination technique of high-performance liquid chromatography (HPLC), a sensitive, selective and simple post-column CL detection method for determining PTU and MTU is described. The optimal conditions for the CL detection and HPLC separation were carried out. The linear ranges were 0.1-20 microg mL(-1) for MTU and 0.1-10 microg mL(-1) for PTU, the detection limits were 0.03 microg mL(-1) for PTU, 0.03 microg mL(-1) for MTU and the quantification limits were 0.1 microg mL(-1) for PTU, 0.1 microg mL(-1) for MTU. The method has been satisfactorily applied for the determination of MTU and PTU in human serum samples.

Detection of glucocorticoid residues in pig liver by high-performance liquid chromatography with on-line electrogenerated [Cu(HIO6)2](5-)--luminol chemiluminescence detection.

A novel method was developed for the simultaneous determination of glucocorticoid residues such as triamcinolone (TR), prednisolone (PR), hydrocortisone (HC), cortisone (CO), methylprednisolone (MP), dexamethasone (DE) and triamcinolone acetonide (TA) by high-performance liquid chromatography (HPLC) coupled with chemiluminescence (CL) detection. The procedure was based on the enhancement effect of glucocorticoids on the chemiluminescence reaction between luminol and the complex of trivalent copper and periodate ([Cu(HIO6)2]5-), which was on-line electrogenerated by constant current electrolysis. The HPLC separation used a Nucleosil RP-C18 column (250 mmx4.6 mm i.d., 5 microm, pore size, 100 A) with a mobile phase consisting of acetonitrile and 1.0 mmol L(-1) ammonium acetate (pH 6.8, 40:60,v/v) at a flow rate of 0.8 mL min(-1). The effects of several parameters on the HPLC resolution and CL emission were studied systematically. Liver samples were hydrolyzed with Helix pomatia juice followed by a solid-phase extraction procedure. Under optimum conditions, the limits of detection (LOD) at a signal-to-noise of 3 ranged from 0.08 to 1.0 ng g(-1) and the limits of quantification (LOQ) at a signal-to-noise of 10 ranged from 0.27 to 3.33 ng g(-1) for seven glucocorticoids. The relative standard deviations (RSD) of intra- and inter-day precision were below 6.8%. The average recoveries for glucocorticoids (spiked at the levels of 5-50 ng g(-1)) in pig liver ranged from 88 to 106%, and the relative standard deviations of the quantitative results were from 2.0 to 6.9%. The proposed method had been successfully applied to the determination of glucocorticoid residues in pig liver.

Detection of indomethacin by high-performance liquid chromatography with in situ electrogenerated Mn(III) chemiluminescence detection.

The determination of indomethacin (INM) in pharmaceutical and biological samples by means of high-performance liquid chromatography (HPLC) with in situ electrogenerated Mn(III) chemiluminescence (CL) detection was proposed. The method was based on the direct CL reaction of INM and Mn(III), which was in situ electrogenerated by constant current electrolysis. The chromatographic separation was carried out on Nucleosil RP-C(18) column (250 mm x 4.6 mm; i.d., 5 microm; pore size, 100 A) at 20 degrees C. The mobile phase consisted of methanol:water:acetic acid=67:33:0.1 solution. At a flow rate of 1.0 mL min(-1), the total run time was 10 min. The effects of several parameters on the HPLC resolution and CL emission were studied systematically. Under the optimal conditions, a linear range from 0.01 to 10 microg mL(-1)(R(2)=0.9991), and a detection limit of 8 ng mL(-1) (signal-to-noise ratio=3) for INM were achieved. The relative standard deviations (R.S.D.) for 0.1 microg mL(-1) INM were 2.2% within a day (n=11) and 3.0% on 5 consecutive days (n=6), respectively. The recovery of INM from urine samples was more than 92%. The applicability of the method for the analysis of pharmaceutical and biological samples was examined.

Development and optimization of an analytical method for the determination of Sudan dyes in hot chilli pepper by high-performance liquid chromatography with on-line electrogenerated BrO- -luminol chemiluminescence detection.

The determination of four Sudan dyes by means of high-performance liquid chromatography (HPLC) with chemiluminescence (CL) detection was proposed. The method was based on the enhancement effect of Sudan dyes on the chemiluminescence reaction between luminol and BrO-, which was on-line electrogenerated by constant current electrolysis. The separation was carried out on Nucleosil RP-C18 column (250 mm x 4.6 mm i.d., 5 microm, pore size, 100 A) at 35 degrees C. The mobile phase consisted of a V (methanol): V (0.2% aqueous formic acid) = 90:10 solution. At a flow-rate of 1.0 ml min(-1), the total run time was 25 min. The effects of several parameters on the HPLC resolution and CL emission were studied systematically. For the four Sudan dyes, the limits of detection (LOD) at a signal-to-noise of 3 ranged from 4 to 8 microg kg(-1) and the limits of quantification (LOQ) at a signal-to-noise of 10 ranged from 13 to 27 microg kg(-1). The relative standard deviations (RSD) of intra-and inter-day precision were below 4.4%. The average recoveries for all four Sudan dyes (spiked at the levels of 1.0 and 1.5 mg kg(-1)) in chilli tomato sauce and hot chilli pepper ranged from 94% to 105%, and the relative standard deviations of the quantitative results were from 2.5 to 4.2%. The proposed method had been successfully applied to the determination of four Sudan dyes in hot chilli products.