Efficient acetoin production from pyruvate by engineered Halomonas bluephagenesis whole-cell biocatalysis

Acetoin is an important platform chemical, which has a wide range of applications in many industries. Halomonas bluephagenesis, a chassis for next generation of industrial biotechnology, has advantages of fast growth and high tolerance to organic acid salts and alkaline environment. Here, α-acetolactate synthase and α-acetolactate decarboxylase from Bacillus subtilis 168 were co-expressed in H. bluephagenesis to produce acetoin from pyruvate. After reaction condition optimization and further increase of α-acetolactate decarboxylase expression, acetoin production and yield were significantly enhanced to 223.4 mmol·L^–1 and 0.491 mol·mol^–1 from 125.4 mmol·L^–1 and 0.333 mol·mol^–1, respectively. Finally, the highest titer of 974.3 mmol·L^–1 (85.84 g·L^–1) of acetoin was accumulated from 2143.4 mmol·L^–1 (188.6 g·L^–1) of pyruvic acid within 8 h in fed-batch bioconversion under optimal reaction conditions. Moreover, the reusability of the cell catalysis was also tested, and the result illustrated that the whole-cell catalysis obtained 433.3, 440.2, 379.0, 442.8 and 339.4 mmol·L^–1 (38.2, 38.8, 33.4, 39.0 and 29.9 g·L^–1) acetoin in five repeated cycles under the same conditions. This work therefore provided an efficient H. bluephagenesis whole-cell catalysis with a broad development prospect in biosynthesis of acetoin.     

A novel flavonol-based colorimetric and turn-on fluorescent probe for rapid determination of hydrazine in real water samples and its bioimaging in vivo andin vitro

Hydrazine is extremely toxic and causes severe harm to human body. Herein, a novel fluorescent probe 4-oxo-2-styryl-4H-chromen-3-yl thiophene-2-carboxylate (FHT) was synthesized for detecting hydrazine by using natural cinnamaldehyde as starting material. This probe exhibited significantly enhanced fluorescence response towards hydrazine over various common metal ions, anions, and amine compounds. The detection limit of probe FHT for hydrazine was as low as 0.14 μmol·L^–1, significantly lower than that of the threshold value of 0.312 μmol·L^–1, imposed by the Environmental Protection Agency. Moreover, the proposed probe was able to detect hydrazine within wide pH (5–10) and linear detection ranges (0–110 μmol·L^–1). This probe was employed for determining trace hydrazine in different environmental water samples. The probe FHT-loaded filter paper strips were able to conveniently detect hydrazine of low concentration through distinct naked-eye and fluorescent color changes. Importantly, the probe FHT with low cytotoxicity was successfully applied to visualize hydrazine in living Hela cells and zebrafish.     

Tuning the electronic structure of NiCoP arrays through V doping for pH-universal hydrogen evolution reaction electrocatalyst

The exploration of cost-effective, high-performance, and stable electrocatalysts for the hydrogen evolution reaction (HER) over wide pH range (0–14) is of paramount importance for future renewable energy conversion technologies. Regulation of electronic structure through doping vanadium atoms is a feasible construction strategy to enhance catalytic activities, electron transfer capability, and stability of the HER electrode. Herein, V-doped NiCoP nanosheets on carbon fiber paper (CFP) (denoted as V_x-NiCoP/CFP) were constructed by doping V modulation on NiCoP nanosheets on CFP and used for pH-universal HER. Benefiting from the abundant catalytic sites and optimized hydrogen binding thermodynamics, the resultant V₁₅-NiCoP/CFP demonstrates a significantly improved HER catalytic activity, requiring overpotentials of 46.5, 52.4, and 85.3 mV to reach a current density of 10 mA·cm^–2 in 1 mol·L^–1 KOH, 0.5 mol·L^–1 H₂SO₄, and 1 mol·L^–1 phosphate buffer solution (PBS) electrolytes, respectively. This proposed cation-doping strategy provides a new inspiration to rationally enhance or design new-type nonprecious metal-based, highly efficient, and pH-universal electrocatalysts for various energy conversion systems.     

Fabrication of high-performance pervaporation composite membrane for alkaline wastewater reclamation

Pervaporation desalination has a unique advantage to recycle concentrated salt solutions. The merit can be applied to treat alkaline wastewater if the membrane has superior alkali-resistance. In this paper, we used polyethylene microfiltration membrane as the substrate and deposited a glutaraldehyde crosslinked sodium carboxymethylcellulose layer by spray-coating. Pervaporation flux of the composite membrane reached 35 ± 2 kg·m^–2·h^–1 with a sodium chloride rejection of 99.9% ± 0.1% when separating a 3.5 wt-% sodium chloride solution at 70 °C. The desalination performance was stable after soaking the membrane in a 20 wt-% NaOH solution at room temperature for 9 d and in a 10 wt-% NaOH solution at 60 °C for 80 h. Moreover, the membrane was stable in 4 wt-% sulfuric acid and a 500 mg·L⁻¹ sodium hypochlorite solution. In a process of concentrating a NaOH solution from 5 to 10 wt-% at 60 °C, an average water flux of 23 kg·m^–2·h^–1 with a NaOH rejection over 99.98% was obtained.     

Novel hierarchical yolk-shell α-Ni(OH)2/Mn2O3 microspheres as high specific capacitance electrode materials for supercapacitors

For high performance supercapacitors, novel hierarchical yolk-shell a-Ni(OH)₂/Mn₂O₃ microspheres were controllably synthesized using a facile two-step method based on the solvothermal treatment. The unique a-Ni(OH)₂ based yolk-shell microstructures decorated with numerous interconnected nanosheets and the hetero-composition features can synergistically enhance reactive site exposure and electron conduction within the microspheres, facilitate charge transfer between electrolyte and electrode materials, and release structural stress during OH⁻ chemisorption/desorption. Moreover, the Mn₂O₃ sediments distributed over the a-Ni(OH)₂ microspheres can serve as an effective protective layer for electrochemical reactions. Consequently, when tested in 1 mol·L⁻¹ KOH aqueous electrolyte for supercapacitors, the yolk-shell a-Ni(OH)₂/Mn₂O₃ microspheres exhibited a considerably high specific capacitance of 2228.6 F·g⁻¹ at 1 A·g⁻¹ and an impressive capacitance retention of 77.7% after 3000 cycles at 10 A·g⁻¹. The proposed a-Ni(OH)₂/Mn₂O₃ microspheres with hetero-composition and unique hierarchical yolk-shell microstructures are highly promising to be used as electrode materials in supercapacitors and other energy storage devices.     

Novel Ag-AgBr decorated composite membrane for dye rejection and photodegradation under visible light

Photocatalytic membranes have received increasing attention due to their excellent separation and photodegradation of organic contaminants in wastewater. Herein, we bound Ag-AgBr nanoparticles onto a synthesized polyacrylonitrile-ethanolamine (PAN-ETA) membrane with the aid of a chitosan (CS)-TiO₂ layer via vacuum filtration and in-situ partial reduction. The introduction of the CS-TiO₂ layer improved surface hydrophilicity and provided attachment sites for the Ag-AgBr nanoparticles. The PAN-ETA/CS-TiO₂/Ag-AgBr photocatalytic membranes showed a relatively high water permeation flux (~ 47 L·m^–2·h^–1·bar^–1) and dyes rejection (methyl orange: 88.22%; congo red: 95%; methyl blue: 97.41%; rose bengal: 99.98%). Additionally, the composite membranes exhibited potential long-term stability for dye/salt separation (dye rejection: ~97%; salt rejection: ~6.5%). Moreover, the methylene blue and rhodamine B solutions (20 mL, 10 mg·L⁻¹) were degraded approximately 90.75% and 96.81% in batch mode via the synthesized photocatalytic membranes under visible light irradiation for 30 min. This study provides a feasible method for the combination of polymeric membranes and inorganic catalytic materials.     

Immobilization of trophic anaerobic acetogen for semi-continuous syngas fermentation

The massive consumption of fossil energy forces people to find new sources of energy. Syngas fermentation has become a hot research field as its high potential in renewable energy production and sustainable development. In this study, trophic anaerobic acetogen Morella thermoacetica was successfully immobilized by calcium alginate embedding method. The ability of the immobilized cells on production of acetic acid through syngas fermentation was compared in both airlift and bubble column bioreactors. The bubble column bioreactor was selected as the better type of bioreactor. The production of acetic acid reached 32.3 g·L^-1 in bubble column bioreactor with a space-time yield of 2.13 g·L^-1·d^-1. The immobilized acetogen could be efficiently reused without significant lag period, even if exposed to air for a short time. A semi-continuous syngas fermentation was performed using immobilized cells, with an average space-time acetic acid yield of 3.20 g·L^-1·d^-1. After 30 days of fermentation, no significant decrease of the acetic acid production rate was observed.     

Formation of CaCO3 hollow microspheres in carbonated distiller waste from Solvay soda ash plants

For decades, distiller waste and CO₂ were not the first choice for production of high valued products. Here, CaCO₃ hollow microspheres, a high-value product was synthesized from such a reaction system. The synthetic methods, the formation mechanism and operational cost were discussed. When 2.5 L·min^–1·L^–1 CO₂ was flowed into distiller waste (pH = 11.4), spheres with 4–13 μm diameters and about 2 μm shell thickness were obtained. It is found that there is a transformation of CaCO₃ particles from solid-cubic nuclei to hollow spheres. Firstly, the Ca(OH)₂ in the distiller waste stimulated the nucleation of calcite with a non-template effect and further maintained the calcite form and prevented the formation of vaterite. Therefore, in absence of auxiliaries, the formation of hollow structures mainly depended on the growth and aging of CaCO₃. Studies on the crystal morphology and its changes during the growth process point to the inside–out Ostwald effect in the formation of hollow spheres. Change in chemical properties of the bulk solution caused changes in interfacial tension and interfacial energy, which promoted the morphological transformation of CaCO₃ particles from cubic calcite to spherical clusters. Finally, the flow process for absorption of CO₂ by distiller waste was designed and found profitable.     

g-C3N4-coated MnO2 hollow nanorod cathode for stable aqueous Zn-ion batteries

Aqueous zinc-ion batteries are attracting considerable attention because of their high safety compared with conventional lithium-ion batteries. Manganese-based materials have been widely developed for zinc-ion batteries cathode owning to their low cost, high security and simple preparation. However, the severe volume expansion and poor stability during charging and discharging limit the further development of manganese-based cathodes. Herein, superior α-MnO₂@g-C₃N₄ was successfully prepared for stable zinc-ion batteries (ZIBs) cathode by introducing g-C₃N₄ nanosheets. Compared with pure α-MnO₂, α-MnO₂@g-C₃N₄ has a specific capacity of 298 mAh·g^–1 at 0.1 A·g^–1. Even at 1 A·g^–1, the α-MnO₂@g-C₃N₄ still retains 100 mAh·g^–1 (83.4% retention after 5000 cycles), implying its excellent cycling stability. The α-MnO₂@g-C₃N₄-based cathode has the highest energy density (563 Wh·kg^–1) and power energy density (2170 W·kg^–1). This work provides new avenues for the development of a wider range of cathode materials for ZIBs.     

Simultaneous harvesting and cell disruption of microalgae using ozone bubbles: optimization and characterization study for biodiesel production

In the present study, ozone was introduced as an alternative approach to harvest and disrupt microalgae cells (Chlorella vulgaris) simultaneously for biodiesel production. At the optimum ozonation conditions (6.14 g·h^–1 ozone concentration, 30 min ozonation time, 1 L·min^–1 of ozone flowrate at medium pH of 10 and temperature of 30 °C), the sedimentation efficiency of microalgae cells increased significantly from 12.56% to 68.62%. It was observed that the microalgae cells aggregated to form flocs after pre-treated with ozone due to the increment of surface charge from –20 to –6.59 mV. Besides, ozone had successfully disrupted the microalgae cells and resulted in efficient lipid extraction, which was 1.9 times higher than the control sample. The extracted microalgae lipid was mainly consisted of methyl palmitate (C16:0), methyl oleate (C18:1) and methyl linolenate (C18:3), making it suitable for biodiesel production. Finally, utilization of recycled culture media after ozonation pre-treatment showed robust growth of microalgae, in which the biomass yield was maintained in the range of 0.796 to 0.879 g·h^–1 for 5 cycles of cultivation.     

Expression and characterization of a CALB-type lipase from Sporisorium reilianum SRZ2 and its potential in short-chain flavor ester synthesis

A lipase from Sporisorium reilianum SRZ2 (SRL) with 73% amino acid sequence identity to Candida antarctica lipase B (CALB) was cloned and overexpressed in Pichia pastoris. The recombinant SRL showed a preference for short-chain p-nitrophenyl esters. It achieved maximum activity at pH 8.0 and 65°C for p-nitrophenyl hexanoate (C6) with K_m and k_cat/K_m values of 0.14 mmol∙L⁻¹ and 1712 min⁻¹∙mmol∙L₋₁ at 30°C, respectively. SRL displayed excellent thermostability and pH stability, retaining more than 79% of its initial activity after incubation at 60°C for 72 h and 75% at pH 3 to 11 for 72 h. It also maintained most of its activity in the presence of inhibitors and detergents except sodium dodecyl sulfate, and it tolerated organic solvents. SRL was covalently immobilized and successfully used for ethyl hexanoate synthesis in cyclohexane or in a solvent-free system with a high conversion yield (>95%). Furthermore, high conversion yield was also achieved for the synthesis of various short-chain flavor esters when high substrate concentrations of 2 mol∙L⁻¹ were applied. This study indicated that a CALB-type lipase from S. reilianum SRZ2 showed great potential in organic ester synthesis.     

污泥含炭吸附剂的制备及其吸附模拟烟气中汞蒸汽的应用(英文)

The carbonaceous adsorbent was prepared from mixtures of dewatered sludge and sawdust with enhanced ZnCl2 chemical activation.Characteristics of the adsorbent were studied using scanning electron microscope(SEM) ,Fourier transform infrared spectroscopy(FT-IR) ,and adsorption of nitrogen.The surface analysis showed that the carbonaceous adsorbent had good specific surface and porosity(394 m 2 ·g-1of BET surface,0.12 and 0.10 ml·g-1of microporous and mesoporous volume,respectively) .The oxygen functional groups such as OH,C O and C O were found on the surface by FTIR and XPS(X-ray photoelectron spectroscopy) .The adsorption of elemental mercury(Hg0) on the carbonaceous adsorbent was studied in a fixed bed reactor.The dynamic adsorption capacity of carbonaceous adsorbent increased with influent mercury concentration,from 23.6μg·g-1at 12.58μg·m-3to 87.9μg·g-1at 72.50μg·m-3,and decreased as the adsorption temperature increased,from 246 μg·g-1 at 25°C to 61.3μg·g-1 at 140°C,when dry nitrogen was used as the carrier gas.The carbonaceous adsorbent presented higher dynamic adsorption capacity than activated carbon,which was 81.2μg·g-1and 53.8μg·g-1respectively.The adsorption data were fitted to the Langmuir adsorption model.The physical and chemical adsorption were identified on the adsorbent.     

Fabrication of high-capacity cation-exchangers for protein adsorption: Comparison of grafting-from and grafting-to approaches

In this work, we have synthesized two polymer-grafted cation exchangers: one via the grafting-from approach, in which sulfopropyl methacrylate (SPM) is grafted through atom transfer radical polymerization onto Sepharose FF (the thus resulting exchanger is referred as Sep-g-SPM), and another via the grafting-to approach, in which the polymer of SPM is directly coupled onto Sepharose FF (the thus resulting exchanger is called as Sep-pSPM). Protein adsorption on these two cation exchangers have been also investigated. At the same ligand density, Sep-g-SPM has a larger accessible pore radius and a smaller depth of polymer layer than Sep-pSPM, due to the controllable introduction of polymer chains with the regular distribution of the ligand. Therefore, high-capacity adsorption of lysozyme and γ-globulin could be achieved simultaneously in Sep-g-SPM with an ionic capacity (IC) of 308 mmol·L^-1. However, Sep-pSPM has an irregular chain distribution and different architecture of polymer layer, which lead to more serious repulsive interaction to proteins, and thus Sep-pSPM has a lower adsorption capacity for γ-globulin than Sep-g-SPM with the similar IC. Moreover, the results from protein uptake experiments indicate that the facilitated transport of adsorbed γ-globulin occurs only in Sep-pSPM and depends on the architecture of polymer layers. Our research provides a clear clue for the development of high-performance protein chromatography.     

Mechanism and kinetics study on removal of Iron from phosphoric acid by cation exchange resin

Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation exchange resin for iron removal from phosphoric acid. The specific surface area and the total exchange capacity of resin were 8.91 m~2·g~(-1) and 5.18 mmol·g~(-1), respectively. The sorption mechanism was determined by FTIR and XPS and the results indicated that iron was combined with-SO_3 H in resin. The removal process was studied as a function of temperature, H_3 PO_4 content and mass ratio between resin and solution. The unit mass of resin to remove iron was 0.058 g·g~(-1) resin when the operating parameters were T = 50 ℃, H_3 PO_4 content = 27.61 wt%and S/L = 0.1, respectively. Kinetics study demonstrated that pseudo-second-order reaction model fits this study best and the calculated activation energy of overall reaction is 29.10 kJ·mol~(-1). The overall reaction process was mainly controlled by pore diffusion.     

Direct synthesis of single-phase α-CaSO4·0.5H2O whiskers from waste nitrate solution

Single-phase α-CaSO₄·0.5H₂O whiskers were directly synthesized from waste Ca(NO₃)₂ solution using a hydrothermal method, and HNO₃ was synchronously regenerated. The effects of reaction temperature and Ca²⁺ concentration on the phase composition and morphology of products were determined by X-ray diffraction and optical microscopy. On the basis of the experimental results, the formation diagram of α-CaSO₄·0.5H₂O was plotted within the range of 5-35 g·L^-1 Ca²⁺ and 115℃-150℃. In addition, the conditions of the direct synthesis of α-CaSO₄·0.5H₂O were determined. Well-crystallized, single-phase α-CaSO₄·0.5H₂O whiskers with high aspect ratios (length, 1785 μm; diameter, 10.63 μm; aspect ratio, 168) and HNO₃ (70.25 g·L^-1) were obtained at the optimal conditions of 25 g·L^-1 Ca²⁺ and 125℃.     

Lithium-based draw solute for forward osmosis to treat wastewater discharged from lithium-ion battery manufacturing

As draw solute is the core element of forward osmosis (FO) technology, here Li-Bet-Tf₂N synthesized from a customized ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf₂N]) and Li₂CO₃ recovered from lithium-ion battery (LIB) wastes is proposed as a novel draw solute to treat Li⁺-containing wastewater from LIB manufacturing through FO filtration. Having high dissociation ability and an extended structure, Li-Bet-Tf₂N generates a sufficiently high osmotic pressure to drive the FO filtration efficiently along with insignificant reverse solute diffusion. Li-Bet-Tf₂N produces a water flux of 21.3 L·(m²·h)⁻¹ at 1.0 mol∙L^–1 against deionized water, surpassing conventional NaCl and MgCl₂ draw solutes with a higher water recovery efficiency and a smaller solute loss. Li-Bet-Tf₂N induces a more stable and higher water permeation flux with a 10.0% water flux decline than NaCl and MgCl₂ for which the water fluxes decline 16.7% and 16.4%, respectively, during the treatment of 2000 mg∙L^–1 Li⁺-containing wastewater for 12 h. More remarkably, unlike other draw solutes which require intensive energy input and complicated processes in recycling, Li-Bet-Tf₂N is easily separated from water via solvent extraction. Reproducible results are achieved with the recycled Li-Bet-Tf₂N. Li-Bet-Tf₂N thus demonstrates a novel class of draw solute with great potentials to treat wastewater economically.     

A DNA sensor based on upconversion nanoparticles and two-dimensional dichalcogenide materials

We demonstrate the fabrication of a new DNA sensor that is based on the optical interactions occurring between oligonucleotide-coated NaYF₄: Yb³⁺; Er³⁺ upconversion nanoparticles and the two-dimensional dichalcogenide materials, MoS₂ and WS₂. Monodisperse upconversion nanoparticles were functionalized with single-stranded DNA endowing the nanoparticles with the ability to interact with the surface of the two-dimensional materials via van der Waals interactions leading to subsequent quenching of the upconversion fluorescence. By contrast, in the presence of a complementary oligonucleotide target and the formation of double-stranded DNA, the upconversion nanoparticles could not interact with MoS₂ and WS₂, thus retaining their inherent fluorescence properties. Utilizing this sensor we were able to detect target oligonucleotides with high sensitivity and specificity whilst reaching a concentration detection limit as low as 5 mol·L^–1, within minutes.     

Using ultrasound to improve the sequential post-synthesis modification method for making mesoporous Y zeolites

Mesoporous Y zeolites were prepared by the sequential chemical dealumination (using chelating agents such as ethylenediaminetetraacetic acid, H₄EDTA, and citric acid aqueous solutions) and alkaline desilication (using sodium hydroxide, NaOH, aqueous solutions) treatments. Specifically, the ultrasound-assisted alkaline treatment (i.e., ultrasonic treatment) was proposed as the alternative to conventional alkaline treatments which are performed under hydrothermal conditions. In comparison with the hydrothermal alkaline treatment, the ultrasonic treatment showed the comparatively enhanced efficiency (with the reduced treatment time, i.e., 5 min vs. 30 min, all with 0.2 mol·L⁻¹ NaOH at 65°C) in treating the dealuminated Y zeolites for creating mesoporosity. For example, after the treatment of a dealuminated zeolite Y (using 0.1 mol·L⁻¹ H₄EDTA at 100°C for 6 h), the ultrasonic treatment produced the mesoporous zeolite Y with the specific external surface area (S_external) of 160 m²·g⁻¹ and mesopore volume (V_meso) of 0.22 cm³·g⁻¹, being slightly higher than that by the conventional method (i.e., S_external = 128 m²·g⁻¹ and V_meso = 0.19 cm³·g⁻¹). The acidic property and catalytic activity (in catalytic cracking of n-octane) of mesoporous Y zeolites obtained by the two methods were comparable. The ultrasonic desilication treatment was found to be generic, also being effective to treat the dealuminated Y zeolites by citric acid. Additionally, the first step of chemical dealumination treatment was crucial to enable the effective creation of mesopores in the parent Y zeolite (with a silicon-to-aluminium ratio, Si/Al= 2.6) regardless of the subsequent alkaline desilication treatment (i.e., ultrasonic or hydrothermal). Therefore, appropriate selection of the condition of the chemical dealumination treatment based on the property of parent zeolites, such as Si/Al ratio and crystallinity, is important for making mesoporous zeolites effectively.