May 2018, Volume 12 Issue 2

Cover illustration

  • (Adam C. Sedgwick, Alex Hayden, Barry Hill, Steven D. Bull, Robert B. P. Elmes, Tony D. James, pp. 311-314)
    The cover shows carrot spacecraft piloted by rabbits.
    Link between the picture and the science contained in the paper: Umbelliferone a coumarin fluorophore was used to prepare the sensor employed in this project and is found in carrots. When our sensor reacts with the nitoreductase (NTR) enzyme it releases the fluorescent blue umbelliferone molecule. Nitrore [Detail] ...

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    Stefania Moioli, Laura A. Pellegrini, Paolo Vergani, Fabio Brignoli

    The growing use of energy by most of world population and the consequent increasing demand for energy are making unexploited low quality gas reserves interesting from an industrial point of view. To meet the required specifications for a natural gas grid, some compounds need to be removed from the sour stream. Because of the high content of undesired compounds (i.e., CO2) in the stream to be treated, traditional purification processes may be too energy intensive and the overall system may result unprofitable, therefore new technologies are under study. In this work, a new process for the purification of natural gas based on a low temperature distillation has been studied, focusing on the dynamics of the system. The robustness of the process has been studied by dynamic simulation of an industrial-scale plant, with particular regard to the performances when operating conditions are changed. The results show that the process can obtain the methane product with a high purity and avoid the solidification of carbon dioxide.

    Ignacio Jorge Castellanos-Beltran, Gnouyaro Palla Assima, Jean-Michel Lavoie

    The methanol-to-olefin (MTO) reaction was investigated in a bench-scale, fixed-bed reactor using an extruded catalyst composed of a commercial SAPO-34 (65 weight percentage, wt-%) embedded in an amorphous SiO2 matrix (35 wt-%). The texture properties, acidity and crystal structure of the pure SAPO-34 and its extruded form (E-SAPO-34) were analyzed and results indicated that the extrusion step did not affect the properties of the catalyst. Subsequently, E-SAPO-34 was tested in a temperature range between 300 and 500 °C, using an aqueous methanol mixture (80 wt-% water content) fed at a weight hour space velocity (WHSV) of 1.21 h−1. At 300 °C, a low conversion was observed combined with catalyst deactivation, which was ascribed to oligomerization and condensation reactions. The coke analysis showed the presence of diamandoid hydrocarbons, which are known to be inactive molecules in the MTO process. At higher temperatures, a quasi-steady state was reached during a 6 h reaction where the optimal temperature was identified at 450 °C, which incidentally led to the lowest coke deposition combined with the highest H/C ratio. Above 450 °C, surges of ethylene and methane were associated to a combination of H-transfer and protolytic cracking reactions. Finally, the present work underscored the convenience of the extrusion technique for testing catalysts at simulated scale-up conditions.

    Si Hyung Jin, Jae-Hoon Jung, Seong-Geun Jeong, Jongmin Kim, Tae Jung Park, Chang-Soo Lee

    Precise control of each individual reaction that constitutes a multistep reaction must be performed to obtain the desired reaction product efficiently. In this work, we present a microfluidic dual loops reactor that enables multistep reaction by integrating two identical loop reactors. Specifically, reactants A and B are synthesized in the first loop reactor and transferred to the second loop reactor to synthesize with reactant C to form the final product. These individual reactions have nano-liter volumes and are carried out in a stepwise manner in each reactor without any cross-contamination issue. To precisely control the mixing efficiency in each loop reactor, we investigate the operating pressure and the operating frequency on the mixing valves for rotary mixing. This microfluidic dual loops reactor is integrated with several valves to realize the fully automated unit operation of a multistep reaction, such as metering the reactants, rotary mixing, transportation, and collecting the product. For proof of concept, CdSeZn nanoparticles are successfully synthesized in a microfluidic dual loops reactor through a fully automated multistep reaction. Taking all of these features together, this microfluidic dual loops reactor is a general microfluidic screening platform that can synthesize various materials through a multistep reaction.

    Hanbin Zheng, Christine Picard, Serge Ravaine

    Nanostructured metal surfaces have been known to exhibit properties that deviate from that of the bulk material. By simply modifying the texture of a metal surface, various unique optical properties can be observed. In this paper, we present a simple two step electrochemical process combining electrodeposition and anodization to generate black gold surfaces. This process is simple, versatile and up-scalable for the production of large surfaces. The black gold films have remarkable optical behavior as they absorb more than 93% of incident light over the entire visible spectrum and also exhibit no specular reflectance. A careful analysis by scanning electron microscopy reveals that these unique optical properties are due to their randomly rough surface, as they consist in a forest of dendritic microstructures with a nanoscale roughness. This new type of black films can be fabricated to a large variety of substrates, turning them to super absorbers with potential applications in photovoltaic solar cells or highly sensitive detectors and so on.

    Yaodong Huang, Shuxue Liu, Zhuofeng Xie, Zipei Sun, Wei Chai, Wei Jiang

    Two new series of 1,2,3-triazole derivatives, with and without iodo substitution, were synthesized and their gelation properties were measured. It was found that the iodo substitution at position 5 of triazole ring could greatly enhance the gelation ability. Scanning electron microscopy and X-ray diffraction reveal that the structures of the organogels from iodo and hydrogenous gelators are totally different. Iodo gels are selectively responsive to the stimuli of Hg2+, whereas hydrogenous gels can respond to Hg2+ and Cu2+. Moreover, the reversible gel-sol transition of hydrogenous gels can be controlled by redox reaction or tuned with suitable chemicals. The single crystal analysis of reference compound (C2) suggests that there are intermolecular and intramolecular non-classical hydrogen bonding interactions but no π-π interaction in hydrogenous gelator. The great difference between the two series of compounds results from the iodo effect and implies the existence of halogen bonding interaction in the iodo compounds.

    Nachuan Wang, Jun Wang, Peng Zhang, Wenbin Wang, Chuangchao Sun, Ling Xiao, Chen Chen, Bin Zhao, Qingran Kong, Baoku Zhu

    A series of amphiphilic copolymers containing poly(vinyl chloride-r-acrylic acid) (P(VC-r-AA) ) was synthesized and used to prepare membranes via a non-solvent induced phase separation method. The prepared membranes were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, and water contact angle and zeta potential measurements. The copolymer P(VC-r-AA) chains did not dissolved in a coagulation bath, indicating that the AA segments were completely retained within the membrane. Enriching degree of AA segments in surface layer was 2 for copolymer membrane. In addition, the introduction of AA segments made the membrane electronegative and hydrophilic so that the membrane was sensitive to the solution pH. The fouling resistance, adsorption of Cu(II), Cr(III) and Ce(IV) ions and the desorption properties of the membranes were also determined. The copolymer membranes exhibited good antifouling performance with a fouling reversibility of 92%. The membranes also had good adsorption capacities for Cu(II), Cr(III) and Ce(IV) ions. The optimal pH for Cu(II) adsorption was 6 and the copolymer membrane has potential applications for low concentration Cu(II) removal.

    Zhe Yang, Xiaoyu Huang, Jianqiang Wang, Chuyang Y. Tang

    Most commercial NF membranes are negatively charged at the pH range of a typical feed solution. In order to enhance the removal of cations (such as Mg2+ or Ca2+), we utilized polyethyleneimine (PEI) and trimesoyl chloride (TMC) to perform interfacial polymerization reaction on a polydopamine coated hydrolyzed polyacrylonitrile substrate to obtain a positively charged nanofiltration membrane. Effects of polydopamine coating time, PEI concentration, TMC reaction time and concentration on the membrane physicochemical properties and separation performance were systematically investigated using scanning electron microscopy, streaming potential and water contact angle measurements. The optimal NF membrane showed high rejection for divalent ions (93.6±2.6% for MgSO4, 92.4±1.3% for MgCl2, and 90.4±2.1% for Na2SO4), accompanied with NaCl rejection of 27.8±2.5% with a permeation flux of 17.2±2.8 L·m2·h1 at an applied pressure of 8 bar (salt concentrations were all 1000 mg·L1). The synthesized membranes showed promising potentials for the applications of water softening.

    Shuai Ma, Huan Zhang, Xiaoyan Dong, Linling Yu, Jie Zheng, Yan Sun

    Amyloid-β (Aβ) protein aggregation is the main hallmark of Alzheimer’s disease (AD). Inhibition of Aβ fibrillation is thus a promising therapeutic approach to the prevention and treatment of AD. Recently, we designed a heptapeptide inhibitor, LVFFARK (LK7). LK7 shows a promising inhibitory capability on Aβ fibrillation, but is prone to self-assembling and displays high cytotoxicity, which would hinder its practical application. Herein, we modified LK7 by a head-to-tail cyclization and obtained a cyclic LK7 (cLK7). cLK7 exhibits a different self-assembly behavior from LK7, and has higher stability against proteolysis than LK7 and little cytotoxicity to SH-SY5Y cells. Thermodynamic analysis revealed that both LK7 and cLK7 could bind to Aβ40 by electrostatic interactions, hydrogen bonding and hydrophobic interactions, but the binding affinity of cLK7 for Aβ40 (KD = 4.96 µmol/L) is six times higher than that of LK7 (KD = 32.2 µmol/L). The strong binding enables cLK7 to stabilize the secondary structure of Aβ40 and potently inhibit its nucleation, fibrillation and cytotoxicity at extensive concentration range, whereas LK7 could only moderately inhibit Aβ40 fibrillation and cytotoxicity at low concentrations. The findings indicate that the peptide cyclization is a promising approach to enhance the performance of peptide-based amyloid inhibitors.

    Bo Chen, Yan Dai, Xuehua Ruan, Yuan Xi, Gaohong He

    Gas membrane separation process is highly unpredictable due to interacting non-ideal factors, such as composition/pressure-dependent permeabilities and real gas behavior. Although molecular dynamic (MD) simulation can mimic those complex effects, it cannot precisely predict bulk properties due to scale limitations of calculation algorithm. This work proposes a method for modeling a membrane separation process for volatile organic compounds by combining the MD simulation with the free volume theory. This method can avoid the scale-up problems of the MD method and accurately simulate the performance of membranes. Small scale MD simulation and pure gas permeation data are employed to correlate pressure-irrelevant parameters for the free volume theory; by this approach, the microscopic effects can be directly linked to bulk properties (non-ideal permeability), instead of being fitted by a statistical approach. A lab-scale hollow fiber membrane module was prepared for the model validation and evaluation. The comparison of model predictions with experimental results shows that the deviations of product purity are reduced from 10% to less than 1%, and the deviations of the permeate and residue flow rates are significantly reduced from 40% to 4%, indicating the reliability of the model. The proposed method provides an efficient tool for process engineering to simulate the membrane recovery process.

    Erigene Bakangura, Yubin He, Xiaolin Ge, Yuan Zhu, Liang Wu, Jin Ran, Congliang Cheng, Kamana Emmanuel, Zhengjin Yang, Tongwen Xu

    Poly(2,6-dimethyl-1,4-phenylene oxide) was tethered with a 1,5-disubstituted tetrazole through a quaternary ammonium linkage. The formation of a tetrazole-ion network in the resulting polymers was found to promote the hydroxide ion transport through the Grotthus-type mechanism.

    Adam C. Sedgwick, Alex Hayden, Barry Hill, Steven D. Bull, Robert B. P. Elmes, Tony D. James

    A simple nitrobenzyl-umbelliferone (NCOU1) was synthesised containing a nitroreductase (NTR) trigger moiety. The presence of NTR, resulted in the fragmentation of the parent molecule and release of the highly emissive fluorophore umbelliferone via an NTR-catalyzed reduction of the nitro group. In the presence of the NTR enzyme, NCOU1 gave rise to a 5-fold increase in fluorescence intensity at 455 nm and was selective for NTR over other reductive enzymes. These results indicate that NCOU1 can be used as a simple assay for the detection of NTR.

    Giorgia De Guido, Matteo Compagnoni, Laura A. Pellegrini, Ilenia Rossetti

    Carbon capture and storage (CCS) have acquired an increasing importance in the debate on global warming as a mean to decrease the environmental impact of energy conversion technologies, by capturing the CO2 produced from the use of fossil fuels in electricity generation and industrial processes. In this respect, post-combustion systems have received great attention as a possible near-term CO2 capture technology that can be retrofitted to existing power plants. This capture technology is, however, energy-intensive and results in large equipment sizes because of the large volumes of the flue gas to be treated. To cope with the demerits of other CCS technologies, the chemical looping combustion (CLC) process has been recently considered as a solution for CO2 separation. It is typically referred to as a technology without energy penalty. Indeed, in CLC the fuel and the combustion air are never mixed and the gases from the oxidation of the fuel (i.e., CO2 and H2O) leave the system as a separate stream and can be separated by condensation of H2O without any loss of energy. The key issue for the CLC process is to find a suitable oxygen carrier, which provides the fuel with the activated oxygen needed for combustion. The aim of this work is to explore the feasibility of using perovskites as oxygen carriers in CLC and to consider the possible advantages with respect to the scrubbing process with amines, a mature post-combustion technology for CO2 separation.