N-Heterocyclic Carbene Silver Complex Modified Polyacrylonitrile Fiber/MIL-101(Cr) Composite as Efficient Chiral Catalyst for Three-Component Coupling Reaction.

Complex asymmetric synthesis can be realized by the chiral induction of amino acids in nature. It is of great significance to design a new biomimetic catalytic system for asymmetric synthesis. In this context, we report the preparation and characterization of the composite of polyacrylonitrile fiber (PANF) and metal-organic framework to catalyze the chiral synthesis of propargylamines. A confined microenvironment is established with N-heterocyclic carbene (NHC) silver complex-supported PANF and D-proline-encapsulated MIL-101(Cr). This novel supported catalyst demonstrated high activity in addition to excellent stereoselectivity in the three-component reaction between alkynes, aldehydes, and amines (A3). The regeneration can be realized by adsorption of D-proline again when the stereoselectivity decreases after recycle uses. By regulating the confined microenvironment on the composite, the activity and selectivity of the catalytic system are improved with turnover numbers of up to 2800 and 98% ee. The biomimetic catalytic system to A3 coupling reaction is systematically studied, and the synergistic catalytic mechanism between NHC-Ag and D-proline in the confined microenvironment is revealed.

A facile covalent strategy for ultrafast negative photoconductance hybrid graphene/porphyrin-based photodetector.

As a powerful complement to positive photoconductance (PPC), negative photoconductance (NPC) holds great potential for photodetector. However, the slow response of NPC relative to PPC devices limits their integration. Here, we propose a facile covalent strategy for an ultrafast NPC hybrid 2D photodetector. Our transistor-based graphene/porphyrin model device with a rise time of 0.2 ms and decay time of 0.3 ms has the fastest response time in the so far reported NPC hybrid photodetectors, which is attributed to efficient photogenerated charge transport and transfer. Both the photosensitive porphyrin with an electron-rich and large rigid structure and the built-in graphene frame with high carrier mobility are prone to the photogenerated charge transport. Especially, the intramolecular donor-acceptor system formed by graphene and porphyrin through covalent bonding promotes photoinduced charge transfer. This covalent strategy can be applied to other nanosystems for high-performance NPC hybrid photodetector.

Selective and Adjustable Removal of Phenolic Compounds from Water by Biquaternary Ammonium Polyacrylonitrile Fibers.

A series of biquaternary ammonium-functionalized fibers were developed to efficiently realize selective removal of phenolic compounds from water. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were employed to determine the successful preparation of functionalized fibers. Scanning electron microscopy, X-ray diffraction (XRD) patterns, and elemental analysis were used to analyze the microstructure and composition. First, the adsorption result shows that a fiber with a three-carbon alkyl chain (PANBQAS-3F) has the maximum adsorption capacity for 2,4-dinitrophenol (2,4-DNP) (406 mg g-1). Electrostatic attraction and π-π interaction are the main forces in adsorption. The adsorption kinetics studies display that PANBQAS-3F can rapidly adsorb 2,4-DNP in 10 min and achieve equilibrium within 20 min. The adsorption process of 2,4-DNP by PANBQAS-3F follows the Langmuir model, demonstrating that the process is more consistent with monolayer adsorption. What is more, the adsorbent PANBQAS-3F can be reused after 10 adsorption/desorption cycles and still maintains an excellent removal rate (99%). Otherwise, PANBQAS-3F was used in a continuous flow process and exhibited a removal rate of more than 96%, which certifies that PANBQAS-3F is an excellent adsorbent and can be utilized in practice.

Synergistic Adsorption for Parabens by an Amphiphilic Functionalized Polypropylene Fiber with Tunable Surface Microenvironment.

A series of novel amphiphilic functionalized fibers with polarity tunable surface microenvironment were constructed by introducing hydrophilic polyamines and hydrophobic linear alkyl chain groups, aiming to selectively remove parabens from water. In addition, Fourier-transform infrared spectroscopy, X-ray powder diffraction, scanning electron microscopy, etc. were employed to determine the successful preparation of amphiphilic functionalized fibers. The adsorption experimental data indicated that the amphiphilic fibers showed excellent selectivity for parabens. In the amphiphilic fibers, hydrogen bonding and hydrophobic interaction existing in one molecular unit can effectively act together to enhance the interaction between substrate and fibers. Kinetic studies illustrated that the adsorption process was a physical adsorption with chemical characteristics. The overall initial adsorption rate together with the stepwise adsorption rate was quantified, and it is inferred that the hydrophobic interaction plays a leading role in the first step of the adsorption process. Moreover, the Freundlich model well described the sorption process with a maximum adsorption of 138.4 mg/g. What's more, the fiber still keeps excellent adsorption capacity (>90%) even after 10 adsorption/desorption cycles, which certifies it is an excellent adsorbent and can be utilized to remove paraben in practice.

Construction of a phosphate-rich polyacrylonitrile fiber surface microenvironment for efficient purification of crystal violet wastewater.

Wastewater purification using fibrous adsorbents has received much attention due to their high efficiency, low cost, and recyclability. In this work, phosphate modified polyacrylonitrile fiber (B-PANEAPF) was prepared and used to remove cationic dyes. The B-PANEAPF showed the best adsorption capacity for crystal violet (CV) when compared with rhodamine B, methyl green, Victoria blue B, methylene blue, and neutral red. The adsorption tests revealed that the fiber possessed high adsorption efficiency and achieved semi-saturated adsorption within 15 min. The maximum adsorption capacity of 354.46 mg g-1 as calculated by the Langmuir adsorption model was higher than many other adsorbents. Furthermore, the B-PANEAPF was used to remove 210 mL of CV in a continuous-flow process with a high removal efficiency over 90%. Besides, the phosphate functionalized fiber could easily decrease the concentration of CV to below 0.5 mg L-1 which is below the maximum effluent discharge standard of 15 mg L-1 prescribed in China. It could also be fully recovered and easily separated from the solution to achieve re-use 10 cycles. Moreover, the adsorption mechanism indicated that the adsorption process of the fiber for CV was mainly attributed to electrostatic interaction and hydrogen bonding. In conclusion, the results suggested that the B-PANEAPF characterized by its simplicity, efficiency, eco-friendliness, and reusability, could be a promising candidate for CV removal.

Highly selective and efficient adsorption of Hg2+ by a recyclable aminophosphonic acid functionalized polyacrylonitrile fiber.

Mercury ions, even an ultra-trace amount in water, present a serious environmental concern. Hence, searching for cost-effective and high-performance Hg2+ adsorbents has acquired increasingly attention but still remained challenging. In this work, aminophosphonic acid was immobilized onto polyacrylonitrile fiber by chemical grafting approaches. The functionalized fiber (PANAPF) possessed high adsorption selectivity and efficiency for Hg2+ when compared with other coexisting ions viz. Pb2+, Cd2+, Ag+, Zn2+, Cu2+, Ni2+, Co2+, Ca2+ and Mg2+. The adsorption results revealed that PANAPF exhibited high removal capacities for Hg2+ over a wide pH range from 3 to 11. The adsorption process was better described by the pseudo second-order kinetic model, indicating the chemical interaction between Hg2+ and active groups on the PANAPF. Moreover, the maximum adsorption capacity as calculated from the Langmuir adsorption model of 358mgg-1 was higher than that of many other adsorbents. The PANAPF could be reused more than 10 times and it is able to decrease Hg2+ below 50µgL-1 which is the maximum discharge standard for mercury containing wastewater in China. A continuous-flow process was also implemented to remove Hg2+. The results suggested the environmentally friendly PANAPF could be a promising candidate for Hg2+ removal in wastewater treatment.

Phosphorylated Polyacrylonitrile Fibers as an Efficient and Greener Acetalization Catalyst.

A novel solid acid catalyst (PANEAP F) is developed by immobilization of phosphoric acid on polyacrylonitrile fiber through covalent bonding. Various characterization techniques such as elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), etc. are utilized to confirm the successful grafting and the stability of the fiber catalysts during application. PANEAP F shows high catalytic activity in the acetalization of aldehydes owing to the high utilization efficiency of its functionalized acid sites. In addition, the strong polarity micro-environment in the surface layers of PANEAP F make it highly suitable for catalytic application in both water and alcohol. Furthermore, the fiber catalyst can be applied to the acetalization of aldehydes in a continuous-flow process at room temperature, and shows excellent reactivity and superior recyclability (over 20 times). The many advantages of PANEAP F such as simple preparation, convenient regulation of acid amount, high durability, and eco-friendly process make it very attractive for fixed-bed reactors in the chemical industry.

An overwhelmingly selective colorimetric sensor for Ag(+) using a simple modified polyacrylonitrile fiber.

A carboxymethyl-dithiocarbamate immobilized polyacrylonitrile fiber colorimetric sensor has been synthesized. This fiber sensor exhibits excellent selectivity and sensitivity for Ag(+) in aqueous solution with a remarkable color change from light pink to red-brown over a wide pH range of 2-12. The sensor responds selectively to Ag(+) in the presence of other ions, including Mg(2+), Al(3+), Ca(2+), Cr(3+), Mn(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pb(2+). The colorimetric sensor has an extremely fast response time (10s) and a low visual limit of detection (5.53×10(-12) mol/L). The fiber sensor also undergoes an obvious color change in the presence of Ag(+) solutions containing EDTA, NaCl or NaBr. Density functional theory optimization reveals that the sensor and Ag(+) interact via a seven-membered ring complexation mechanism.

Bifunctional polyacrylonitrile fiber-mediated conversion of sucrose to 5-hydroxymethylfurfural in mixed-aqueous systems.

A highly efficient catalytic system composed of a bifunctional polyacrylonitrile fiber (PANF-PA[BnBr]) and a metal chloride was employed to produce 5-hydroxymethylfurfural (HMF) from sucrose in mixed-aqueous systems. The promoter of PANF-PA[BnBr] incorporates protonic acid groups that promote the hydrolysis of the glycosidic bond to convert sucrose into glucose and fructose, and then catalyzes fructose dehydration to HMF, while the ammonium moiety may promote synergetically with the metal chloride the isomerization of glucose to fructose and transfer HMF from the aqueous to the organic phase. The detailed characterization by elemental analysis, FTIR spectroscopy, and SEM confirmed the rangeability of the fiber promoter during the modification and utilization processes. Excellent results in terms of high yield (72.8%) of HMF, superior recyclability (6 cycles) of the process, and effective scale-up and simple separation procedures of the catalytic system were obtained. Moreover, the prominent features (high strength, good flexibility, etc.) of the fibers are very attractive for fix-bed reactor.

Localization and function of the membrane-bound riboflavin in the Na+-translocating NADH:quinone oxidoreductase (Na+-NQR) from Vibrio cholerae.

The sodium ion-translocating NADH:quinone oxidoreductase (Na(+)-NQR) from the human pathogen Vibrio cholerae is a respiratory membrane protein complex that couples the oxidation of NADH to the transport of Na(+) across the bacterial membrane. The Na(+)-NQR comprises the six subunits NqrABCDEF, but the stoichiometry and arrangement of these subunits are unknown. Redox-active cofactors are FAD and a 2Fe-2S cluster on NqrF, covalently attached FMNs on NqrB and NqrC, and riboflavin and ubiquinone-8 with unknown localization in the complex. By analyzing the cofactor content and NADH oxidation activity of subcomplexes of the Na(+)-NQR lacking individual subunits, the riboflavin cofactor was unequivocally assigned to the membrane-bound NqrB subunit. Quantitative analysis of the N-terminal amino acids of the holo-complex revealed that NqrB is present in a single copy in the holo-complex. It is concluded that the hydrophobic NqrB harbors one riboflavin in addition to its covalently attached FMN. The catalytic role of two flavins in subunit NqrB during the reduction of ubiquinone to ubiquinol by the Na(+)-NQR is discussed.

Oxidant-induced formation of a neutral flavosemiquinone in the Na+-translocating NADH:Quinone oxidoreductase (Na+-NQR) from Vibrio cholerae.

The Na(+)-translocating NADH:quinone oxidoreductase (Na(+)-NQR) from the human pathogen Vibrio cholerae is a respiratory flavo-FeS complex composed of the six subunits NqrA-F. The Na(+)-NQR was produced as His(6)-tagged protein by homologous expression in V. cholerae. The isolated complex contained near-stoichiometric amounts of non-covalently bound FAD (0.78 mol/mol Na(+)-NQR) and riboflavin (0.70 mol/mol Na(+)-NQR), catalyzed NADH-driven Na(+) transport (40 nmol Na(+)min(-1) mg(-1)), and was inhibited by 2-n-heptyl-4-hydroxyquinoline-N-oxide. EPR spectroscopy showed that Na(+)-NQR as isolated contained very low amounts of a neutral flavosemiquinone (10(-3) mol/mol Na(+)-NQR). Reduction with NADH resulted in the formation of an anionic flavosemiquinone (0.10 mol/mol Na(+)-NQR). Subsequent oxidation of the Na(+)-NQR with ubiquinone-1 or O(2) led to the formation of a neutral flavosemiquinone (0.24 mol/mol Na(+)-NQR). We propose that the Na(+)-NQR is fully oxidized in its resting state, and discuss putative schemes of NADH-triggered redox transitions.

The Na+-translocating NADH:quinone oxidoreductase (Na+-NQR) from Vibrio cholerae enhances insertion of FeS in overproduced NqrF subunit.

The Na+-translocating NADH:quinone oxidoreductase (Na+-NQR) from Vibrio cholerae is a membrane-bound, respiratory Na+ pump. Its NqrF subunit contains one FAD and a [2Fe-2S] cluster and catalyzes the initial oxidation of NADH. A soluble variant of NqrF lacking its hydrophobic, N-terminal helix (NqrF') was produced in V. cholerae wild type and nqr deletion strain. Under identical conditions of growth and induction, the yield of NqrF' increased by 30% in the presence of the Na+-NQR. FAD-containing NqrF' species with or without the FeS cluster were observed, indicating that assembly of the FeS center, but not insertion of the flavin cofactor, was limited during overproduction in V. cholerae. A comparison of these distinct NqrF' species with regard to specific NADH dehydrogenase activity, pH dependence of activity and thermal inactivation showed that NqrF' lacking the [2Fe-2S] cluster was less stable, partially unfolded, and therefore prone to proteolytic degradation in V. cholerae. We conclude that the overall yield of NqrF' critically depends on the amount of fully assembled, FeS-containing NqrF' in the V. cholerae host cells. The Na+-NQR is proposed to increase the stability of NqrF' by stimulating the maturation of FeS centers.

Crystallization of the NADH-oxidizing domain of the Na+-translocating NADH:ubiquinone oxidoreductase from Vibrio cholerae.

The Na+-translocating NADH:quinone oxidoreductase (Na+-NQR) from pathogenic and marine bacteria is a respiratory complex that couples the exergonic oxidation of NADH by quinone to the transport of Na+ across the membrane. The NqrF subunit oxidizes NADH and transfers the electrons to other redox cofactors in the enzyme. The FAD-containing domain of NqrF has been expressed, purified and crystallized. The purified NqrF FAD domain exhibited high rates of NADH oxidation and contained stoichiometric amounts of the FAD cofactor. Initial crystallization of the flavin domain was achieved by the sitting-drop technique using a Cartesian MicroSys4000 robot. Optimization of the crystallization conditions yielded yellow hexagonal crystals with dimensions of 30 x 30 x 70 microm. The protein mainly crystallizes in long hexagonal needles with a diameter of up to 30 microm. Crystals diffract to 2.8 A and belong to space group P622, with unit-cell parameters a = b = 145.3, c = 90.2 A, alpha = beta = 90, gamma = 120 degrees.